Isostructural rubidium and caesium 4-(3,5-di­nitro­pyrazol-4-yl)-3,5-di­nitro­pyrazolates: crystal engineering with polynitro energetic species

In the structures of the title salts, two independent cations (Rb, Cs) are situated on a crystallographic twofold axis and on a center of inversion, respectively. Mutual inter­molecular hydrogen bonding between the conjugate 3,5-dinito­pyrazole NH-donor and 3,5-di­nitro­pyrazolate N-acceptor sites of the anions governs the self-assembly of the translation-related anions in a predictable fashion. The anionic chains are further linked by multiple ion–dipole inter­actions involving the 12-coordinate cations bonded to two pyrazole N-atoms and all of the eight nitro O-atoms. The resulting ionic networks follow the CsCl topological archetype, with either metal or organic ions residing in an environment of eight counter-ions. Weak lone pair–π-hole inter­actions are also relevant to the packing.

Abstract

In the structures of the title salts, poly[[μ₄-4-(3,5-di­nitro­pyrazol-4-yl)-3,5-di­nitro­pyrazol-1-ido]rubidium], [Rb(C₆HN₈O₈)] _n , (1), and its isostructural caesium analogue [Cs(C₆HN₈O₈) _n , (2), two independent cations M1 and M2 (M = Rb, Cs) are situated on a crystallographic twofold axis and on a center of inversion, respectively. Mutual inter­molecular hydrogen bonding between the conjugate 3,5-dinito­pyrazole NH-donor and 3,5-di­nitro­pyrazole N-acceptor sites of the anions [N⋯N = 2.785 (2) Å for (1) and 2.832 (3) Å for (2)] governs the self-assembly of the translation-related anions in a predictable fashion. Such one-component modular construction of the organic subtopology supports the utility of the crystal-engineering approach towards designing the structures of polynitro energetic materials. The anionic chains are further linked by multiple ion–dipole inter­actions involving the 12-coordinate cations bonded to two pyrazole N-atoms [Rb—N = 3.1285 (16), 3.2261 (16) Å; Cs—N = 3.369 (2), 3.401 (2) Å] and all of the eight nitro O-atoms [Rb—O = 2.8543 (15)–3.6985 (16) Å; Cs—O = 3.071 (2)–3.811 (2) Å]. The resulting ionic networks follow the CsCl topological archetype, with either metal or organic ions residing in an environment of eight counter-ions. Weak lone pair–π-hole inter­actions [pyrazole-N atoms to NO₂ groups; N⋯N = 2.990 (3)–3.198 (3) Å] are also relevant to the packing. The Hirshfeld surfaces and percentage two-dimensional fingerprint plots for (1) and (2) are described.

Chemical context

Many issues of crystal engineering, in regard to control over bonding patterns, supra­molecular topologies, mol­ecular packing, and crystal morphologies are highly relevant to the area of energetic materials. In particular, non-covalent contacts involving common explosophore nitro groups (Bauzá et al., 2017 ▸) establish pathways to transmit inter­molecular inter­actions and they are often responsible for higher densities of the solids (Zhang et al., 2000 ▸). The layered architectures of the energetic solids provide better buffering against external mechanical stimuli, which is essential for developing insens­itive materials (Zhang et al., 2008 ▸). At the same time, incorp­oration of specific coordination geometries for the assembly of metal–organic solids offers potential for the synthesis of new perchlorate-free flame colorants and pyrotechnics (Glück et al., 2017 ▸). However, successful applications of the crystal-engineering methodology toward designing the structures of polynitro compounds are relatively rare, so far (Domasevitch et al., 2020 ▸). This is predetermined by a lack of reliable supra­molecular synthons comprising the nitro groups, which are only weak acceptors of conventional hydrogen bonds (Robinson et al., 2000 ▸) and are only weak donors with respect to the metal ions. A more severe limitation is associated with the need for direct bonding between the nitro-rich functionalities only, since the incorporation of any low-energetic component or solvent mol­ecules is an inevitable penalty to the performance. Such dilution of the energetic moieties in the crystals is relevant, for example, to a series of hydrogen-bonded solids prepared by Aakeröy et al. (2015 ▸) with acidic ethyl­enedinitramine and common bitopic pyridine-N bases.

Recently, we have reported a new strategy for the construction of energetic salts, which offers higher degree of control over the structure. Double functionality of the well-performing material 3,3′,5,5′-tetra­nitro-4,4′-bi­pyrazole [H₂(TNBP)] (Domasevitch et al., 2019 ▸) grants synthetic access either to singly or doubly anionic species [{H(TNBP)}⁻ and {TNBP}²⁻, respectively]. The former combine conjugate di­nitro­pyrazole donor and di­nitro­pyrazolate acceptor sites for sustaining particularly strong N—H⋯N bonding. In fact, such bonding of two explosophores dominated the self-assembly in a very predictable fashion and it was traced in all of the previously examined salts with a range of nitro­gen-rich cations (Gospodinov et al., 2020 ▸). That the resulting networks are ionic may find further applications to the synthesis of inorganic nitro-rich salts, based upon Li⁺, Rb⁺, Cs⁺, Sr²⁺, Ba²⁺ and other s- and p-block cations, which are a new generation of ‘green’ pyrotechnic formulations (Steinhauser & Klapötke, 2008 ▸).

Following the above findings, we now describe the synthesis and structure of rubidium and caesium 4-(3,5-di­nitro­pyrazol-4-yl)-3,5-di­nitro­pyrazolates M{H(TNBP)} [M = Rb (1) and Cs (2)], incorporating the peculiar half-deprotonated bi­pyrazole tectons. These materials may give an insight into the development of flame colorants in pyrotechnics: rubidium and caesium compounds exhibit, respectively, purple and orange colors when burned.

Structural commentary

The title compounds are isostructural, crystallizing in space group C2/c. The mol­ecular structure of the rubidium salt (1) is shown in Fig. 1 ▸, with the unique part comprising one organic anion {H(TNBP)}⁻ (or C₆HN₈O₈ ⁻) and two cations situated on a crystallographic twofold axis [Rb1] or on a center of inversion [Rb2]. The easy formation of such salts is con­ditioned by the appreciable acidity of polynitro­pyrazoles, c.f. pK _a = 3.14 for 3,5-di­nitro­pyrazole versus 14.63 for the parent pyrazole (Janssen et al., 1973 ▸), while for the crystallization of singly charged hydrogen bipyrazolate derivatives, the weakly polarizing, large Rb⁺ and Cs⁺ cations are important.

Figure 1.

The mol­ecular structure and the atom-labeling scheme for (1) [the atom labeling for (2) is identical, with Cs1 and Cs2 instead of Rb1 and Rb2], with displacement ellipsoids drawn at the 50% probability level and the N—H⋯N hydrogen bond shown as a dashed line. [Symmetry code: (i) x, y + 1, z.]

Both unique metal ions exhibit exceptionally high coord­in­ation numbers of twelve, which are completed with ten O atoms [Rb—O = 2.8543 (15)–3.6985 (16) Å; Cs—O 3.071 (2)–3.811 (2) Å] and two N atoms of the pyrazole rings [Rb—N = 3.1285 (16) and 3.2261 (16) Å; Cs—N = 3.369 (2) and 3.401 (2) Å] (Tables 1 ▸ and 2 ▸). Most of these separations slightly exceed the sum of the corresponding ionic radii [which are M—O = 3.13 and 3.28 Å; M—N = 3.18 and 3.34 Å for 12-coordinate Rb and Cs ions, respectively (Shannon, 1976 ▸)], indicating the weakness of these relatively distal ion–dipole inter­actions. This may be best related to the bonding in the ionic salts with polynitro anions lacking conventional donor sites. For example, in caesium picrate, the cations display a comparable 12-fold coordination and a wide spread of Cs—O separations of 3.028 (3)–3.847 (2) Å (Schouten et al., 1990 ▸). The coordination polyhedra of the two unique cations are very similar and represent essentially distorted icosa­hedra (Fig. 2 ▸). These are completed with a twofold axis [for M1] or inversion [for M2] related pairs of chelating nitro­pyrazole-N,O groups, pseudo-chelating NO₂ groups and two singly coordinated NO₂ groups. Both kinds of cations reside in a closest environment of eight {H(TNBP)}⁻ anions, which maintain supra­molecular boxes with a small inter­nal cavity for the cation (Fig. 3 ▸). It is notable that all of the eight O atoms present and the two pyrazole N atoms coordinate to the metal ions.

Table 1. Selected bond lengths (Å) for (1) .

Rb1—O1i	2.8543 (15)	Rb2—O5iii	2.9616 (17)
Rb1—O5	2.9673 (16)	Rb2—O7	2.9690 (15)
Rb1—N3	3.1285 (16)	Rb2—O3i	3.0743 (17)
Rb1—O8ii	3.3074 (16)	Rb2—N2i	3.2261 (16)
Rb1—O3iii	3.424 (2)	Rb2—O6iii	3.2275 (16)
Rb1—O4iii	3.4942 (16)	Rb2—O2ii	3.6985 (16)

Symmetry codes: (i) x, y+1, z; (ii) -x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z; (iii) -x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}.

Table 2. Selected bond lengths (Å) for (2) .

Cs1—O1i	3.071 (2)	Cs2—O7	3.109 (2)
Cs1—O5	3.177 (2)	Cs2—O5ii	3.159 (2)
Cs1—O3ii	3.351 (3)	Cs2—O3i	3.297 (2)
Cs1—N3	3.369 (2)	Cs2—O6ii	3.396 (2)
Cs1—O4ii	3.464 (2)	Cs2—N2i	3.401 (2)
Cs1—O8iii	3.514 (2)	Cs2—O2iv	3.811 (2)

Symmetry codes: (i) x, y+1, z; (ii) -x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}; (iii) -x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z; (iv) x-{\script{1\over 2}}, y+{\script{1\over 2}}, z.

Figure 2.

Twelvefold coordination environments adopted by the Rb1 and Rb2 ions in (1), in the form of distorted icosa­hedra. The coordination of the two Cs ions in (2) is almost identical. [Symmetry codes: (i) x, y + 1, z; (ii) −x +  , y +  , −z +  ; (iii) −x +  , −y +  , −z; (iv) x −  , y +  , z; (v) −x + 1, y + 1, −z +  ; (vi) −x + 1, y, −z +  ; (vii) x +  , y +  , z; (viii) x +  , −y +  , z +  ; (ix) −x, −y + 1, −z; (x) x −  , −y +  , z −  ; (xi) −x, −y, −z.]

Figure 3.

The Rb2 ion resides inside a supra­molecular prism (represented here as a gray box) adopted by eight anions, which complete the coordination environment. The vertices of the prism are built through the mid-points of the central C—C bonds of the mol­ecules. The environments of Rb1 and the respective Cs ions in the structure of (2) are similar. [Symmetry codes: (i) x, y + 1, z; (ii) −x +  , y +  , −z +  ; (iv) x −  , y +  , z; (ix) −x, −y + 1, −z.]

The main geometrical parameters of the organic anions are very similar to those of the parent [H₂(TNBP)] (Domasevitch et al., 2019 ▸). In the case of (1), the protolytic inequivalency of two pyrazole halves is reflected by the ring C—N distances, which are almost the same for anionic ring A (atoms C4/C5/C6/N3/N4) [N3—C4 = 1.343 (2) and N4—C6 1.348 (2) Å] and are slightly differentiated for the neutral ring B (C1/C2/C3/N1/N2) [N1—C1 1.348 (2) and N2—C3 1.331 (2) Å] (Fig. 1 ▸). In addition, the deprotonation causes slight elongation of the N—N bond, which is 1.336 (2) Å for ring B and 1.347 (2) Å for ring A. Even more sensitive parameters are the bond angles at the N atoms, which are perceptibly different for the former fragment [N2—N1—C1 = 110.67 (15); C3—N2—N1 = 104.29 (15)°], being much closer for the latter [106.38 (15) and 107.59 (15)°]. In the case of (2), the corresponding geometries are nearly identical for rings A and B [C—N = 1.340 (3)–1.346 (3) Å; N2—N1—C1 = 109.8 (2); N3—N4—C6 = 109.6 (2)° and N1—N2—C3 = 104.9 (2); N4—N3—C4 = 105.1 (2)°]. This situation agrees with the disorder of the H atoms between two positions [at the N1 or N4 carrier atoms] within the N—H⋯N hydrogen bond in (2) as discussed below.

In both structures, the {H(TNBP)}⁻ anions display twisted conformations, with the dihedral angles between the rings being 42.99 (8) and 44.86 (10)° for (1) and (2), respectively. These angles, however, are unusually small. For example, typical parameters for the structurally similar 3,3′,5,5′-tetra­methyl-4,4′-bi­pyrazole unit are 65–90° (Ponomarova et al., 2013 ▸). The flattening of the {H(TNBP)}⁻ anion suggests certain attractivity in steric inter­actions of the NO₂ groups, which generates a set of short intra­molecular O⋯N contacts, the shortest being O2⋯N7 at 2.786 (3) Å observed for (2). Indeed, the nitro/nitro stackings are energetically favorable, as a special kind of lone pair–π-hole bond (Bauzá et al., 2017 ▸).

Supra­molecular features

The ionic structures of the title compounds may be regarded as three-dimensional networks, which are related to the structure of CsCl. The metal ions themselves constitute a distorted primitive cubic framework with the cells representing elongated prisms [the M⋯M edges are 5.2560 (3), 6.5962 (3), 8.8395 (8) and 5.4775 (4), 6.3932 (5), 9.1482 (12) Å for (1) and (2), respectively]. Every such cell is populated with the organic anion and, conversely, every cation resides inside the distorted prismatic box of eight anions (Figs. 3 ▸ and 4 ▸).

Figure 4.

Fragment of the crystal structure of (1), showing the polar hydrogen-bonded anionic chains propagating along the b-axis direction, in the environment of the Rb cations. Blue lines indicate a pseudo-primitive cubic net arrangement of the cations, with every cell populated by a single anion (c.f. the structure of CsCl). [Symmetry codes: (i) x, y + 1, z; (vi) −x + 1, y, −z +  ; (xiv) x, y − 1, z.]

Beyond Coulombic attraction, the principal supra­molecular inter­action is strong and directional N—H⋯N hydrogen bonding between the pyrazole and pyrazolate halves of translation-related anions [N1⋯N4^xiv = 2.785 (2) and 2.832 (3) Å; H⋯N^xiv = 1.93 and 1.99 Å; N1H⋯N4^xiv = 166 and 163° for (1) and (2), respectively; symmetry code: (xiv) x, y − 1, z], arranging the latter into linear polar chains propagating along the b-axis direction (Fig. 4 ▸). Such bonding involving the conjugate acid (pyrazole-NH) and base (pyrazolate-N) sites is a very rare, if not the only, example of a highly reliable supra­molecular synthon for crystal engineering with energetic polynitro derivatives. In fact, the conjugate inter­actions are relevant for many organic species, e.g. carboxyl­ates (Speakman, 1972 ▸) and oximes (Domasevitch et al., 1998 ▸), being often the most crucial bonding for the crystal patterns. With the aid of such a synthon, the assembly of the organic subtopology of lower dimensionality is possible in a very rational and predictable fashion and the title structures exactly follow the motifs of previously examined NH₃OH⁺ and 3,3′,5,5′-tetra­methyl-4,4′-bipyrazolium {H(TNBP)}⁻ salts (Gospodinov et al., 2020 ▸).

The above hydrogen-bonded chains associate to yield layers lying parallel to the ac plane and the latter are separated by the layers of metal cations (Fig. 5 ▸). There are two kinds of weaker inter­actions, which facilitate close packing of the chains. The first of these is identified by close N3⋯N6ⁱⁱ and N2⋯N7^xii contacts [the shortest of 2.990 (3) Å] originating in situation of the pyrazole N atoms almost exactly above the NO₂ N atoms (Table 3 ▸). This peculiar lone pair–π-hole inter­action occurs instead of the more common NO₂/NO₂ bonding (Bauzá et al., 2017 ▸), which is also relevant for the structure of [H₂(TNBP)] itself (Domasevitch et al., 2019 ▸). One can note that extensive ion-dipole inter­actions M⋯O₂N in (1) and (2) mitigate against mutual inter­actions of nitro groups, which are totally eliminated from the suite of supra­molecular bonds. The second type of inter­chain inter­action is stacking between pairs of inversion-related pyrazole and pyrazolate rings (Fig. 6 ▸), with the O7 and N5 atoms situated nearly above the centroids of the rings A ⁱⁱⁱ and B ^xiii, respectively [symmetry codes: (iii) −x +  , −y +  , −z; (xiii) −x +  , −y −  , −z.] (Table 4 ▸). As a result of the inversion symmetry of the stacks, the alignment of two polar hydrogen-bonded chains in (1) is anti­parallel, while the above lone pair–π-hole inter­actions support coherent alignment of the contributing chains (Fig. 6 ▸). This results in pairing of the chains possessing identical polarities (Fig. 5 ▸). In the structure of (2), the polarity of the chains is eliminated because of the disorder of the H atoms in the N—H⋯N/N⋯H—N bonds.

Figure 5.

Structure of (1) viewed in projection on the ac plane (down the direction of the anionic chains) showing the organic layers, which are separated by layers of the cations. The chains of opposite polarity are identified by blue and red colors. [Symmetry codes: (iv) x −  , y +  , z; (v) −x + 1, y + 1, −z +  .]

Table 3. Geometry of lone pair–π-hole inter­actions (Å, °) in (1) and (2).

N⋯plane is a distance of an N-donor to the mean plane of a nitro group and φ is an angle of the N⋯N axis to the plane of the nitro group.

Compound	N-Donor	Group	N⋯N	N⋯plane	φ
(1)	N2	(C4N7O5O6)xii	2.997 (3)	2.980 (2)	83.9 (2)
	N3	(C3N6O3O4)ii	3.198 (3)	3.093 (2)	75.3 (2)
(2)	N2	(C4N7O5O6)xii	2.990 (3)	2.976 (3)	84.5 (2)
	N3	(C3N6O3O4)ii	3.186 (3)	3.083 (3)	75.4 (2)

Symmetry codes: (ii) −x + {1\over 2}, y + {1\over 2}, −z + {1\over 2}; (xii) −x + {1\over 2}, y − {1\over 2}, −z + {1\over 2}.

Figure 6.

A suite of non-covalent inter­actions of the {H(TNBP)}⁻ anions, with two kinds of lone pair–π-hole bonds (marked in red) and two kinds of nitro/pyrazole stacks (marked in blue) complementing the conventional hydrogen bonding. [Symmetry codes: (ii) −x +  , y +  , −z +  ; (v) −x + 1, y + 1, −z +  ; (vi) −x + 1, y, −z +  ; (xiii) −x +  , −y −  , −z; (xiv) x, y − 1, z.]

Table 4. Geometry of stacking inter­actions involving nitro and pyrazole groups (Å, °) in (1) and (2).

Atom⋯Cg is the shortest distance from the nitro group atom to the centroid of the ring; Atom⋯plane is the deviation of the given atom from the mean plane of the ring and φ is the angle of the atom⋯Cg axis to the plane of the ring.

Compound	Atom	Ring	Atom⋯Cg	Atom⋯plane	φ
(1)	O7	(C4C5C6N3N4)iii	3.265 (3)	3.262 (2)	87.5 (2)
	N5	(C1C2C3N1N2)xiii	3.541 (3)	3.526 (3)	84.7 (2)
(2)	O7	(C4C5C6N3N4)iii	3.240 (3)	3.232 (3)	86.0 (3)
	N5	(C1C2C3N1N2)xiii	3.448 (3)	3.389 (3)	79.4 (3)

Symmetry codes: (iii) −x + {1\over 2}, −y + {1\over 2}, −z; (xiii) −x + {1\over 2}, −y − {1\over 2}, −z.

Hirshfeld analysis

The supra­molecular inter­actions in the title structures were also assessed by Hirshfeld surface analysis (Spackman & Byrom, 1997 ▸; McKinnon et al., 2004 ▸; Hirshfeld, 1977 ▸; Spackman & McKinnon, 2002 ▸) performed with CrystalExplorer17 (Turner et al., 2017 ▸). The contributions of different kinds of inter­atomic contacts to the Hirshfeld surfaces of the individual anions are listed in Table 5 ▸ and the fingerprint plots for (1) are shown in Fig. 7 ▸. The most significant contributors are O⋯O contacts (37.4%), while the fraction of O,N⋯Rb (15.4%) is relatively modest due to the larger lengths of the ion–dipole inter­actions. The shortest O⋯O separation on the plot of ∼2.8 Å corresponds to the contact O1⋯O8^xiii = 2.741 (2) Å [2.732 (3) Å in (2); symmetry code (xiii) −x +  , −y −  , −z]. We note that slight contraction of the O⋯M fraction in the case of M = Rb [13.6% for (1) and 13.0% for (2)] coincides with a larger contribution of less favorable O⋯O contacts [37.4% for (1) and 35.5% for (2)]. This may be an additional factor destabilizing the structure: the crystals of (1) eventually decompose under the mother solution, unlike the stable Cs analogue. The lone pair–π-hole pyrazole-NO₂ inter­actions generate 5.3% (1) and 6.3% (2) of the contacts of the Hirshfeld surfaces, with the shortest N⋯N = 2.9 Å. The nature of the O⋯N/N⋯O and N⋯C/C⋯N contacts [in total 23.3% (1) and 22.8% (2)] is similar, since they correspond to the stacking of pyrazole and NO₂ groups with shortest O⋯N and N⋯C distances of 3.2 and 3.3 Å, respectively. However, there are no pairs of the features that are characteristic for the mutual O⋯N/N⋯O inter­actions of NO₂ groups themselves (Domasevitch et al., 2020 ▸). The contributions of the O⋯H/H⋯O and N⋯H/H⋯N contacts are comparable and perceptible [5.4 and 6.9% for (1) and 5.2 and 6.6% for (2)], but only the latter correspond to hydrogen bonding, as is reflected in the plots. These bonds are responsible for a pair of very sharp features pointing to the lower left, with a shortest contact of 1.9 Å, whereas O⋯H/H⋯O contacts are identified only with a diffuse collection of points between the above features and with a shortest contact of 2.8 Å.

Table 5. Contributions of the different kinds of the contacts (%) to the Hirshfeld surfaces of individual anions in (1) ^a and (2).

M = Rb (1) and Cs (2)

Contact	(1)	(2)
O⋯M	13.0	13.6
N⋯M	2.4	2.2
O⋯O	37.4	35.5
N⋯N	5.3	6.3
C⋯C	1.0	0.7
O⋯N/N⋯O	15.8	16.2
O⋯C/C⋯O	3.8	5.4
N⋯C/C⋯N	7.5	6.6
N⋯H/H⋯N	6.9	6.6
O⋯H/H⋯O	5.4	5.2
C⋯H/H⋯C	1.5	1.7

Note: (a) For the two-dimensional plots for (1), see Fig. 7 ▸.

Figure 7.

Two-dimensional fingerprint plots for the individual anions in (1), and delineated into the principal contributions of O,N⋯Rb, O⋯O, N⋯N, O⋯N/N⋯O, O⋯C/C⋯O, N⋯C/C⋯C, N⋯H/H⋯N and O⋯H/H⋯O contacts. Other contacts are C⋯H/H⋯C (1.5%) and C⋯C (1.0%).

Synthesis and crystallization

3,3′,5,5′-Tetra­nitro-4,4′-bi­pyrazole [H₂(TNBP)] was synthesized in 92% yield by nitration of 4,4′-bi­pyrazole in mixed acids and then crystallized from water as a monohydrate (Domasevitch et al., 2019 ▸).

To prepare the Rb salt (1), 0.332 g (1.0 mmol) of H₂(TNBP)·H₂O was added to a solution of 0.116 g (0.5 mmol) of Rb₂CO₃ in 8 ml of water and the mixture was heated at 353–363 K until total dissolution was observed. The solution was cooled to room temperature and left for a few hours for crystallization. Pale-yellow crystals of Rb{H(TNBP)} were isolated in a yield of 0.325 g (82%) and dried in air. The compound is unstable when stored under the reaction solution as the initially formed crystals dissolve in a period of 10–15 d and colorless H₂(TNBP)·H₂O deposits. In a similar way, the reaction of 0.332 g (1.0 mmol) of H₂(TNBP)·H₂O and 0.163 g (0.5 mmol) of Cs₂CO₃ in 8 ml of water gives 0.415 g (93%) of pale-yellow Cs{H(TNBP)} (2). Unlike (1), this material is stable under the mother solution. Similar reactions with Na₂CO₃ and K₂CO₃ did not afford any hydrogen bipyrazolates and led to soluble M ₂{TNBP} (M = Na, K) and precipitation of the excess amount of H₂(TNBP)·H₂O.

Analysis (%) calculated for (1), C₆HN₈O₈Rb: C 18.08, H 0.25, N 28.12; found: C 17.93, H 0.44, N 28.49. IR (KBr, cm⁻¹): 590 w, 708 w, 838 m, 854 s, 996 m, 1024 m, 1308 s, 1352 vs, 1398 vs, 1432 m, 1490 vs, 1500 m, 1556 vs, 1636 w, 3448 br.

Analysis (%) calculated for (2), C₆HCsN₈O₈: C 16.15, H 0.23, N 25.13; found: C 16.01, H 0.38, N 28.11. IR (KBr, cm⁻¹): 516 w, 586 m, 708 m, 838 s, 852 s, 994 s, 1022 m, 1170 w, 1306 s, 1324 s, 1350 vs, 1396 vs, 1432 s, 1488 vs, 1512 vs, 1544 vs, 1634 m, 3024 br, 3442 br.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 6 ▸. The hydrogen atoms were located and then refined as riding with N—H = 0.87 Å and U _iso(H) = 1.5U _eq(N). For (2), the H atom is equally disordered over two positions corresponding to the N1 and N4 carrier atoms.

Table 6. Experimental details.

	(1)	(2)
Crystal data
Chemical formula	[Rb(C6HN8O8)]	[Cs(C6HN8O8)]
M r	398.62	446.06
Crystal system, space group	Monoclinic, C2/c	Monoclinic, C2/c
Temperature (K)	213	213
a, b, c (Å)	19.4400 (15), 8.6070 (4), 16.0977 (10)	19.944 (2), 8.6307 (7), 16.2083 (17)
β (°)	115.264 (7)	113.766 (8)
V (Å3)	2435.8 (3)	2553.4 (5)
Z	8	8
Radiation type	Mo Kα	Mo Kα
μ (mm−1)	4.13	2.97
Crystal size (mm)	0.20 × 0.16 × 0.14	0.20 × 0.16 × 0.14
Data collection
Diffractometer	Stoe IPDS	Stoe IPDS
Absorption correction	Numerical [X-RED (Stoe & Cie, 2001 ▸) and X-SHAPE (Stoe & Cie, 1999 ▸)]	Numerical [X-RED (Stoe & Cie, 2001 ▸) and X-SHAPE (Stoe & Cie, 1999 ▸)]
T min, T max	0.672, 0.789	0.677, 0.772
No. of measured, independent and observed [I > 2σ(I)] reflections	9925, 2890, 2186	9014, 2990, 2686
R int	0.033	0.042
(sin θ/λ)max (Å−1)	0.658	0.656
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.026, 0.055, 0.89	0.027, 0.060, 1.21
No. of reflections	2890	2990
No. of parameters	210	211
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.37, −0.39	0.67, −0.77

Computer programs: IPDS Software (Stoe & Cie, 2000 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2018/1 (Sheldrick, 2015 ▸), DIAMOND (Brandenburg, 1999 ▸) and WinGX (Farrugia, 2012 ▸).

Supplementary Material

CCDC references: 2113578, 2113577

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Poly[[µ₄-4-(3,5-dinitropyrazol-4-yl)-3,5-dinitropyrazol-1-ido]rubidium] (1) . Crystal data

[Rb(C6HN8O8)]	F(000) = 1552
Mr = 398.62	Dx = 2.174 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.4400 (15) Å	Cell parameters from 8000 reflections
b = 8.6070 (4) Å	θ = 2.3–27.9°
c = 16.0977 (10) Å	µ = 4.13 mm−1
β = 115.264 (7)°	T = 213 K
V = 2435.8 (3) Å3	Prism, yellow
Z = 8	0.20 × 0.16 × 0.14 mm

Poly[[µ₄-4-(3,5-dinitropyrazol-4-yl)-3,5-dinitropyrazol-1-ido]rubidium] (1) . Data collection

Stoe IPDS diffractometer	2186 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.033
φ oscillation scans	θmax = 27.9°, θmin = 2.3°
Absorption correction: numerical [X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]	h = −25→25
Tmin = 0.672, Tmax = 0.789	k = −10→11
9925 measured reflections	l = −20→20
2890 independent reflections

Poly[[µ₄-4-(3,5-dinitropyrazol-4-yl)-3,5-dinitropyrazol-1-ido]rubidium] (1) . Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.055	H-atom parameters constrained
S = 0.89	w = 1/[σ2(Fo2) + (0.0326P)2] where P = (Fo2 + 2Fc2)/3
2890 reflections	(Δ/σ)max < 0.001
210 parameters	Δρmax = 0.37 e Å−3
0 restraints	Δρmin = −0.39 e Å−3

Poly[[µ₄-4-(3,5-dinitropyrazol-4-yl)-3,5-dinitropyrazol-1-ido]rubidium] (1) . 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.

Poly[[µ₄-4-(3,5-dinitropyrazol-4-yl)-3,5-dinitropyrazol-1-ido]rubidium] (1) . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Rb1	0.500000	0.39279 (3)	0.250000	0.02840 (9)
Rb2	0.000000	0.500000	0.000000	0.03230 (9)
O1	0.38330 (9)	−0.38304 (18)	0.16106 (14)	0.0422 (5)
O2	0.38489 (9)	−0.14611 (18)	0.11639 (13)	0.0344 (4)
O3	0.03697 (9)	−0.16032 (19)	0.06215 (16)	0.0490 (5)
O4	0.10681 (9)	0.03244 (17)	0.13792 (13)	0.0347 (4)
O5	0.45319 (8)	0.09854 (18)	0.30718 (12)	0.0329 (4)
O6	0.37797 (9)	−0.09294 (16)	0.29580 (11)	0.0301 (4)
O7	0.13123 (9)	0.34370 (17)	−0.01293 (13)	0.0344 (4)
O8	0.12218 (8)	0.09417 (17)	−0.03095 (11)	0.0280 (3)
N1	0.23222 (9)	−0.36612 (17)	0.10737 (13)	0.0199 (4)
H1	0.247444	−0.461154	0.107308	0.030*
N2	0.16218 (9)	−0.32601 (19)	0.09532 (13)	0.0210 (4)
N3	0.33470 (9)	0.27100 (18)	0.19547 (13)	0.0207 (4)
N4	0.26946 (9)	0.31935 (17)	0.12643 (13)	0.0200 (4)
N5	0.35387 (9)	−0.25662 (18)	0.13349 (12)	0.0212 (4)
N6	0.09790 (10)	−0.0935 (2)	0.10011 (14)	0.0266 (4)
N7	0.39083 (9)	0.03467 (19)	0.27152 (13)	0.0218 (4)
N8	0.15509 (9)	0.21089 (19)	0.01062 (13)	0.0206 (4)
C1	0.27606 (10)	−0.2391 (2)	0.11965 (14)	0.0175 (4)
C2	0.23545 (10)	−0.1061 (2)	0.11814 (14)	0.0161 (4)
C3	0.16475 (10)	−0.1719 (2)	0.10251 (15)	0.0181 (4)
C4	0.32927 (10)	0.1159 (2)	0.19966 (14)	0.0177 (4)
C5	0.26131 (10)	0.0553 (2)	0.13416 (14)	0.0158 (4)
C6	0.22651 (10)	0.1926 (2)	0.08941 (14)	0.0167 (4)

Poly[[µ₄-4-(3,5-dinitropyrazol-4-yl)-3,5-dinitropyrazol-1-ido]rubidium] (1) . Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Rb1	0.01707 (13)	0.01962 (14)	0.0442 (2)	0.000	0.00897 (13)	0.000
Rb2	0.02226 (15)	0.03355 (17)	0.0307 (2)	0.00090 (12)	0.00132 (12)	−0.01165 (14)
O1	0.0311 (8)	0.0188 (8)	0.0702 (14)	0.0128 (6)	0.0153 (9)	0.0038 (8)
O2	0.0284 (8)	0.0279 (8)	0.0533 (12)	−0.0005 (6)	0.0234 (8)	0.0034 (8)
O3	0.0212 (8)	0.0283 (9)	0.0941 (17)	−0.0011 (7)	0.0214 (9)	0.0036 (9)
O4	0.0411 (9)	0.0214 (8)	0.0519 (12)	0.0071 (7)	0.0299 (9)	−0.0003 (7)
O5	0.0206 (7)	0.0336 (8)	0.0327 (10)	−0.0044 (6)	0.0001 (7)	0.0048 (7)
O6	0.0375 (8)	0.0155 (7)	0.0272 (10)	−0.0001 (6)	0.0040 (7)	0.0046 (6)
O7	0.0313 (8)	0.0190 (7)	0.0470 (12)	0.0121 (6)	0.0111 (8)	0.0127 (7)
O8	0.0225 (7)	0.0231 (8)	0.0305 (10)	−0.0046 (6)	0.0037 (6)	0.0008 (7)
N1	0.0231 (8)	0.0089 (7)	0.0267 (11)	0.0004 (6)	0.0098 (7)	−0.0010 (7)
N2	0.0222 (8)	0.0127 (8)	0.0283 (11)	−0.0004 (6)	0.0109 (7)	0.0020 (7)
N3	0.0220 (8)	0.0141 (8)	0.0230 (10)	−0.0016 (6)	0.0067 (7)	−0.0010 (7)
N4	0.0213 (8)	0.0103 (7)	0.0277 (11)	−0.0001 (6)	0.0098 (7)	0.0009 (7)
N5	0.0211 (8)	0.0164 (8)	0.0230 (10)	0.0031 (6)	0.0064 (7)	−0.0051 (7)
N6	0.0256 (9)	0.0174 (9)	0.0423 (13)	0.0030 (7)	0.0198 (8)	0.0077 (8)
N7	0.0241 (9)	0.0176 (9)	0.0196 (10)	0.0010 (6)	0.0053 (7)	−0.0014 (7)
N8	0.0187 (8)	0.0180 (8)	0.0263 (11)	0.0031 (6)	0.0108 (7)	0.0057 (7)
C1	0.0203 (9)	0.0115 (9)	0.0193 (12)	0.0001 (7)	0.0070 (8)	0.0000 (7)
C2	0.0187 (9)	0.0104 (8)	0.0188 (11)	0.0010 (7)	0.0075 (8)	0.0008 (8)
C3	0.0203 (9)	0.0122 (9)	0.0223 (12)	0.0008 (7)	0.0095 (8)	0.0019 (8)
C4	0.0206 (9)	0.0119 (8)	0.0192 (11)	0.0007 (7)	0.0070 (8)	−0.0003 (7)
C5	0.0177 (9)	0.0109 (8)	0.0202 (12)	0.0014 (7)	0.0094 (8)	0.0003 (7)
C6	0.0185 (9)	0.0126 (8)	0.0198 (11)	0.0016 (7)	0.0089 (8)	0.0011 (7)

Poly[[µ₄-4-(3,5-dinitropyrazol-4-yl)-3,5-dinitropyrazol-1-ido]rubidium] (1) . Geometric parameters (Å, º)

Rb1—O1i	2.8543 (15)	O1—N5	1.221 (2)
Rb1—O1ii	2.8543 (15)	O2—N5	1.219 (2)
Rb1—O5	2.9673 (16)	O3—N6	1.220 (2)
Rb1—O5iii	2.9673 (16)	O4—N6	1.219 (2)
Rb1—N3	3.1285 (16)	O5—N7	1.228 (2)
Rb1—N3iii	3.1285 (16)	O6—N7	1.227 (2)
Rb1—O8iv	3.3074 (16)	O7—N8	1.231 (2)
Rb1—O8v	3.3074 (16)	O8—N8	1.225 (2)
Rb1—O3vi	3.424 (2)	N1—N2	1.336 (2)
Rb1—O3vii	3.424 (2)	N1—C1	1.348 (2)
Rb1—O4vi	3.4942 (16)	N1—H1	0.8700
Rb1—O4vii	3.4942 (16)	N2—C3	1.331 (2)
Rb2—O5viii	2.9616 (17)	N3—C4	1.343 (2)
Rb2—O5vii	2.9616 (17)	N3—N4	1.347 (2)
Rb2—O7ix	2.9690 (15)	N4—C6	1.348 (2)
Rb2—O7	2.9690 (15)	N5—C1	1.440 (2)
Rb2—O3x	3.0743 (17)	N6—C3	1.450 (2)
Rb2—O3ii	3.0743 (17)	N7—C4	1.441 (2)
Rb2—N2x	3.2261 (16)	N8—C6	1.435 (3)
Rb2—N2ii	3.2261 (16)	C1—C2	1.384 (3)
Rb2—O6viii	3.2275 (16)	C2—C3	1.406 (3)
Rb2—O6vii	3.2275 (16)	C2—C5	1.462 (2)
Rb2—O2v	3.6985 (16)	C4—C5	1.393 (3)
Rb2—O2xi	3.6985 (16)	C5—C6	1.399 (3)
O1i—Rb1—O1ii	94.94 (7)	O5vii—Rb2—O6viii	139.46 (4)
O1i—Rb1—O5	134.80 (5)	O7ix—Rb2—O6viii	71.28 (5)
O1ii—Rb1—O5	116.69 (4)	O7—Rb2—O6viii	108.72 (5)
O1i—Rb1—O5iii	116.69 (4)	O3x—Rb2—O6viii	86.34 (5)
O1ii—Rb1—O5iii	134.80 (5)	O3ii—Rb2—O6viii	93.66 (5)
O5—Rb1—O5iii	62.80 (7)	N2x—Rb2—O6viii	59.09 (4)
O1i—Rb1—N3	150.29 (5)	N2ii—Rb2—O6viii	120.91 (4)
O1ii—Rb1—N3	65.44 (5)	O5viii—Rb2—O6vii	139.46 (4)
O5—Rb1—N3	52.18 (4)	O5vii—Rb2—O6vii	40.54 (4)
O5iii—Rb1—N3	92.36 (4)	O7ix—Rb2—O6vii	108.72 (5)
O1i—Rb1—N3iii	65.44 (5)	O7—Rb2—O6vii	71.28 (5)
O1ii—Rb1—N3iii	150.29 (5)	O3x—Rb2—O6vii	93.66 (5)
O5—Rb1—N3iii	92.36 (4)	O3ii—Rb2—O6vii	86.34 (5)
O5iii—Rb1—N3iii	52.18 (4)	N2x—Rb2—O6vii	120.91 (4)
N3—Rb1—N3iii	140.85 (6)	N2ii—Rb2—O6vii	59.09 (4)
O1i—Rb1—O8iv	52.19 (5)	O6viii—Rb2—O6vii	180.00 (7)
O1ii—Rb1—O8iv	124.56 (5)	O5viii—Rb2—O2v	63.14 (4)
O5—Rb1—O8iv	82.76 (4)	O5vii—Rb2—O2v	116.86 (4)
O5iii—Rb1—O8iv	100.60 (4)	O7ix—Rb2—O2v	127.24 (4)
N3—Rb1—O8iv	119.65 (4)	O7—Rb2—O2v	52.75 (4)
N3iii—Rb1—O8iv	61.84 (4)	O3x—Rb2—O2v	105.45 (5)
O1i—Rb1—O8v	124.56 (5)	O3ii—Rb2—O2v	74.55 (5)
O1ii—Rb1—O8v	52.19 (5)	N2x—Rb2—O2v	126.63 (4)
O5—Rb1—O8v	100.60 (4)	N2ii—Rb2—O2v	53.37 (4)
O5iii—Rb1—O8v	82.76 (4)	O6viii—Rb2—O2v	74.96 (4)
N3—Rb1—O8v	61.84 (4)	O6vii—Rb2—O2v	105.04 (4)
N3iii—Rb1—O8v	119.65 (4)	O5viii—Rb2—O2xi	116.86 (4)
O8iv—Rb1—O8v	176.11 (5)	O5vii—Rb2—O2xi	63.14 (4)
O1i—Rb1—O3vi	96.42 (5)	O7ix—Rb2—O2xi	52.76 (4)
O1ii—Rb1—O3vi	93.94 (5)	O7—Rb2—O2xi	127.25 (4)
O5—Rb1—O3vi	111.58 (4)	O3x—Rb2—O2xi	74.55 (5)
O5iii—Rb1—O3vi	53.44 (4)	O3ii—Rb2—O2xi	105.45 (5)
N3—Rb1—O3vi	106.56 (4)	N2x—Rb2—O2xi	53.37 (4)
N3iii—Rb1—O3vi	68.00 (4)	N2ii—Rb2—O2xi	126.63 (4)
O8iv—Rb1—O3vi	128.33 (4)	O6viii—Rb2—O2xi	105.04 (4)
O8v—Rb1—O3vi	52.33 (4)	O6vii—Rb2—O2xi	74.96 (4)
O1i—Rb1—O3vii	93.94 (5)	O2v—Rb2—O2xi	180.00 (3)
O1ii—Rb1—O3vii	96.42 (5)	N5—O1—Rb1xii	158.96 (13)
O5—Rb1—O3vii	53.44 (4)	N6—O3—Rb2xii	130.77 (13)
O5iii—Rb1—O3vii	111.58 (4)	N6—O3—Rb1xiii	91.12 (15)
N3—Rb1—O3vii	68.00 (4)	Rb2xii—O3—Rb1xiii	107.84 (5)
N3iii—Rb1—O3vii	106.56 (4)	N6—O4—Rb1xiii	87.86 (12)
O8iv—Rb1—O3vii	52.33 (4)	N7—O5—Rb2xiv	99.33 (12)
O8v—Rb1—O3vii	128.33 (4)	N7—O5—Rb1	127.55 (12)
O3vi—Rb1—O3vii	164.66 (6)	Rb2xiv—O5—Rb1	124.88 (5)
O1i—Rb1—O4vi	60.41 (5)	N7—O6—Rb2xiv	86.64 (11)
O1ii—Rb1—O4vi	91.65 (5)	N8—O7—Rb2	128.40 (13)
O5—Rb1—O4vi	141.47 (4)	N8—O8—Rb1v	121.64 (12)
O5iii—Rb1—O4vi	78.75 (4)	N2—N1—C1	110.67 (15)
N3—Rb1—O4vi	137.39 (5)	N2—N1—H1	124.7
N3iii—Rb1—O4vi	59.64 (4)	C1—N1—H1	124.7
O8iv—Rb1—O4vi	102.96 (4)	C3—N2—N1	104.29 (15)
O8v—Rb1—O4vi	75.66 (4)	C3—N2—Rb2xii	119.80 (12)
O3vi—Rb1—O4vi	36.38 (4)	N1—N2—Rb2xii	132.66 (12)
O3vii—Rb1—O4vi	153.75 (4)	C4—N3—N4	106.38 (15)
O1i—Rb1—O4vii	91.65 (5)	C4—N3—Rb1	114.35 (12)
O1ii—Rb1—O4vii	60.41 (5)	N4—N3—Rb1	128.37 (12)
O5—Rb1—O4vii	78.75 (4)	N3—N4—C6	107.59 (15)
O5iii—Rb1—O4vii	141.47 (4)	O2—N5—O1	125.25 (17)
N3—Rb1—O4vii	59.64 (4)	O2—N5—C1	118.13 (15)
N3iii—Rb1—O4vii	137.39 (5)	O1—N5—C1	116.61 (16)
O8iv—Rb1—O4vii	75.66 (4)	O4—N6—O3	124.73 (18)
O8v—Rb1—O4vii	102.96 (4)	O4—N6—C3	117.74 (17)
O3vi—Rb1—O4vii	153.75 (4)	O3—N6—C3	117.50 (18)
O3vii—Rb1—O4vii	36.38 (4)	O4—N6—Rb1xiii	72.68 (11)
O4vi—Rb1—O4vii	139.76 (5)	O3—N6—Rb1xiii	69.40 (14)
O5viii—Rb2—O5vii	180.00 (8)	C3—N6—Rb1xiii	132.87 (13)
O5viii—Rb2—O7ix	108.32 (4)	O6—N7—O5	123.15 (18)
O5vii—Rb2—O7ix	71.68 (4)	O6—N7—C4	118.54 (16)
O5viii—Rb2—O7	71.68 (4)	O5—N7—C4	118.29 (16)
O5vii—Rb2—O7	108.32 (4)	O6—N7—Rb2xiv	72.15 (11)
O7ix—Rb2—O7	180.0	O5—N7—Rb2xiv	59.69 (11)
O5viii—Rb2—O3x	57.45 (5)	C4—N7—Rb2xiv	146.67 (12)
O5vii—Rb2—O3x	122.55 (5)	O8—N8—O7	123.57 (18)
O7ix—Rb2—O3x	111.42 (4)	O8—N8—C6	118.40 (15)
O7—Rb2—O3x	68.58 (4)	O7—N8—C6	118.00 (17)
O5viii—Rb2—O3ii	122.55 (5)	N1—C1—C2	110.36 (16)
O5vii—Rb2—O3ii	57.45 (5)	N1—C1—N5	119.62 (15)
O7ix—Rb2—O3ii	68.58 (4)	C2—C1—N5	130.01 (16)
O7—Rb2—O3ii	111.42 (4)	C1—C2—C3	100.20 (16)
O3x—Rb2—O3ii	180.00 (10)	C1—C2—C5	129.17 (17)
O5viii—Rb2—N2x	64.39 (4)	C3—C2—C5	130.53 (17)
O5vii—Rb2—N2x	115.61 (4)	N2—C3—C2	114.47 (16)
O7ix—Rb2—N2x	63.20 (4)	N2—C3—N6	117.47 (16)
O7—Rb2—N2x	116.80 (4)	C2—C3—N6	127.90 (17)
O3x—Rb2—N2x	50.09 (4)	N3—C4—C5	113.82 (17)
O3ii—Rb2—N2x	129.91 (4)	N3—C4—N7	117.80 (17)
O5viii—Rb2—N2ii	115.61 (4)	C5—C4—N7	128.31 (17)
O5vii—Rb2—N2ii	64.39 (4)	C4—C5—C6	99.63 (15)
O7ix—Rb2—N2ii	116.80 (4)	C4—C5—C2	129.27 (17)
O7—Rb2—N2ii	63.20 (4)	C6—C5—C2	131.10 (17)
O3x—Rb2—N2ii	129.91 (4)	N4—C6—C5	112.57 (17)
O3ii—Rb2—N2ii	50.09 (4)	N4—C6—N8	119.01 (16)
N2x—Rb2—N2ii	180.0	C5—C6—N8	128.38 (16)
O5viii—Rb2—O6viii	40.54 (4)
C1—N1—N2—C3	−1.3 (2)	C1—C2—C3—N2	0.0 (2)
C1—N1—N2—Rb2xii	157.43 (14)	C5—C2—C3—N2	−176.6 (2)
C4—N3—N4—C6	−1.0 (2)	C1—C2—C3—N6	175.2 (2)
Rb1—N3—N4—C6	140.39 (14)	C5—C2—C3—N6	−1.4 (4)
Rb1xii—O1—N5—O2	26.7 (6)	O4—N6—C3—N2	154.3 (2)
Rb1xii—O1—N5—C1	−153.8 (4)	O3—N6—C3—N2	−24.1 (3)
Rb1xiii—O4—N6—O3	48.3 (2)	Rb1xiii—N6—C3—N2	62.6 (3)
Rb1xiii—O4—N6—C3	−129.88 (17)	O4—N6—C3—C2	−20.8 (3)
Rb2xii—O3—N6—O4	−164.56 (17)	O3—N6—C3—C2	160.8 (2)
Rb1xiii—O3—N6—O4	−49.6 (2)	Rb1xiii—N6—C3—C2	−112.5 (2)
Rb2xii—O3—N6—C3	13.7 (3)	N4—N3—C4—C5	0.3 (2)
Rb1xiii—O3—N6—C3	128.59 (17)	Rb1—N3—C4—C5	−147.15 (14)
Rb2xii—O3—N6—Rb1xiii	−114.92 (19)	N4—N3—C4—N7	−177.06 (17)
Rb2xiv—O6—N7—O5	32.5 (2)	Rb1—N3—C4—N7	35.5 (2)
Rb2xiv—O6—N7—C4	−145.49 (16)	O6—N7—C4—N3	156.77 (19)
Rb2xiv—O5—N7—O6	−36.3 (2)	O5—N7—C4—N3	−21.3 (3)
Rb1—O5—N7—O6	174.67 (14)	Rb2xiv—N7—C4—N3	55.7 (3)
Rb2xiv—O5—N7—C4	141.67 (15)	O6—N7—C4—C5	−20.2 (3)
Rb1—O5—N7—C4	−7.3 (3)	O5—N7—C4—C5	161.7 (2)
Rb1—O5—N7—Rb2xiv	−149.01 (17)	Rb2xiv—N7—C4—C5	−121.3 (2)
Rb1v—O8—N8—O7	22.7 (3)	N3—C4—C5—C6	0.4 (2)
Rb1v—O8—N8—C6	−155.32 (13)	N7—C4—C5—C6	177.5 (2)
Rb2—O7—N8—O8	72.4 (3)	N3—C4—C5—C2	−179.85 (19)
Rb2—O7—N8—C6	−109.63 (17)	N7—C4—C5—C2	−2.8 (4)
N2—N1—C1—C2	1.4 (2)	C1—C2—C5—C4	−41.0 (4)
N2—N1—C1—N5	−179.72 (17)	C3—C2—C5—C4	134.7 (2)
O2—N5—C1—N1	157.8 (2)	C1—C2—C5—C6	138.7 (2)
O1—N5—C1—N1	−21.7 (3)	C3—C2—C5—C6	−45.6 (4)
O2—N5—C1—C2	−23.6 (3)	N3—N4—C6—C5	1.3 (2)
O1—N5—C1—C2	156.9 (2)	N3—N4—C6—N8	−176.64 (16)
N1—C1—C2—C3	−0.8 (2)	C4—C5—C6—N4	−1.0 (2)
N5—C1—C2—C3	−179.5 (2)	C2—C5—C6—N4	179.2 (2)
N1—C1—C2—C5	175.8 (2)	C4—C5—C6—N8	176.7 (2)
N5—C1—C2—C5	−2.9 (4)	C2—C5—C6—N8	−3.1 (4)
N1—N2—C3—C2	0.8 (2)	O8—N8—C6—N4	168.87 (18)
Rb2xii—N2—C3—C2	−161.31 (14)	O7—N8—C6—N4	−9.2 (3)
N1—N2—C3—N6	−174.94 (18)	O8—N8—C6—C5	−8.7 (3)
Rb2xii—N2—C3—N6	23.0 (2)	O7—N8—C6—C5	173.2 (2)

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

Poly[[µ₄-4-(3,5-dinitropyrazol-4-yl)-3,5-dinitropyrazol-1-ido]rubidium] (1) . Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N4xii	0.87	1.93	2.785 (2)	166

Symmetry code: (xii) x, y−1, z.

Poly[[µ₄-4-(3,5-dinitropyrazol-4-yl)-3,5-dinitropyrazol-1-ido]caesium] (2) . Crystal data

[Cs(C6HN8O8)]	F(000) = 1696
Mr = 446.06	Dx = 2.321 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.944 (2) Å	Cell parameters from 8000 reflections
b = 8.6307 (7) Å	θ = 2.2–27.8°
c = 16.2083 (17) Å	µ = 2.97 mm−1
β = 113.766 (8)°	T = 213 K
V = 2553.4 (5) Å3	Prism, yellow
Z = 8	0.20 × 0.16 × 0.14 mm

Poly[[µ₄-4-(3,5-dinitropyrazol-4-yl)-3,5-dinitropyrazol-1-ido]caesium] (2) . Data collection

Stoe IPDS diffractometer	2686 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.042
φ oscillation scans	θmax = 27.8°, θmin = 2.2°
Absorption correction: numerical [X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]	h = −20→26
Tmin = 0.677, Tmax = 0.772	k = −11→11
9014 measured reflections	l = −21→21
2990 independent reflections

Poly[[µ₄-4-(3,5-dinitropyrazol-4-yl)-3,5-dinitropyrazol-1-ido]caesium] (2) . Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.027	H-atom parameters constrained
wR(F2) = 0.060	w = 1/[σ2(Fo2) + (0.0214P)2 + 3.932P] where P = (Fo2 + 2Fc2)/3
S = 1.21	(Δ/σ)max < 0.001
2990 reflections	Δρmax = 0.67 e Å−3
211 parameters	Δρmin = −0.77 e Å−3
0 restraints	Extinction correction: SHELXL2018/1 (Sheldrick 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00151 (14)

Poly[[µ₄-4-(3,5-dinitropyrazol-4-yl)-3,5-dinitropyrazol-1-ido]caesium] (2) . 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.

Poly[[µ₄-4-(3,5-dinitropyrazol-4-yl)-3,5-dinitropyrazol-1-ido]caesium] (2) . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cs1	0.500000	0.42703 (3)	0.250000	0.03031 (9)
Cs2	0.000000	0.500000	0.000000	0.04080 (10)
O1	0.36906 (14)	−0.3754 (3)	0.1294 (2)	0.0536 (7)
O2	0.38087 (12)	−0.1274 (2)	0.12176 (15)	0.0369 (5)
O3	0.04269 (12)	−0.1420 (3)	0.07349 (18)	0.0460 (6)
O4	0.11168 (14)	0.0488 (2)	0.14521 (17)	0.0391 (5)
O5	0.44367 (12)	0.1085 (2)	0.29706 (15)	0.0379 (5)
O6	0.36857 (13)	−0.0765 (2)	0.29226 (14)	0.0351 (5)
O7	0.13940 (12)	0.3610 (2)	−0.01257 (15)	0.0391 (5)
O8	0.12142 (13)	0.1123 (2)	−0.02282 (14)	0.0370 (5)
N1	0.22944 (13)	−0.3511 (2)	0.10259 (15)	0.0260 (5)
H1A	0.243307	−0.445633	0.099377	0.039*	0.5
N2	0.16260 (13)	−0.3095 (2)	0.09520 (15)	0.0267 (5)
N3	0.32972 (13)	0.2858 (2)	0.19322 (15)	0.0266 (5)
N4	0.26741 (13)	0.3309 (2)	0.12597 (15)	0.0252 (5)
H1B	0.256042	0.426103	0.108253	0.038*	0.5
N5	0.34581 (13)	−0.2427 (2)	0.12310 (15)	0.0260 (5)
N6	0.10201 (14)	−0.0772 (3)	0.10736 (17)	0.0304 (5)
N7	0.38266 (14)	0.0482 (3)	0.26693 (15)	0.0268 (5)
N8	0.15723 (13)	0.2273 (2)	0.01333 (15)	0.0253 (5)
C1	0.27188 (15)	−0.2249 (3)	0.11572 (17)	0.0228 (5)
C2	0.23398 (15)	−0.0903 (3)	0.11868 (16)	0.0216 (5)
C3	0.16581 (15)	−0.1553 (3)	0.10518 (17)	0.0236 (5)
C4	0.32386 (15)	0.1316 (3)	0.19768 (17)	0.0230 (5)
C5	0.25873 (14)	0.0703 (3)	0.13417 (16)	0.0208 (5)
C6	0.22504 (15)	0.2064 (3)	0.08996 (17)	0.0230 (5)

Poly[[µ₄-4-(3,5-dinitropyrazol-4-yl)-3,5-dinitropyrazol-1-ido]caesium] (2) . Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cs1	0.02186 (13)	0.02958 (13)	0.03945 (15)	0.000	0.01232 (10)	0.000
Cs2	0.02484 (14)	0.04935 (19)	0.03776 (16)	−0.00107 (11)	0.00175 (11)	−0.01535 (12)
O1	0.0407 (13)	0.0213 (10)	0.095 (2)	0.0120 (10)	0.0230 (14)	−0.0019 (12)
O2	0.0366 (12)	0.0257 (10)	0.0524 (13)	0.0006 (9)	0.0220 (10)	0.0023 (9)
O3	0.0277 (11)	0.0353 (11)	0.0727 (16)	−0.0002 (10)	0.0177 (11)	0.0033 (11)
O4	0.0456 (13)	0.0234 (10)	0.0604 (14)	0.0040 (9)	0.0339 (12)	−0.0020 (9)
O5	0.0276 (11)	0.0354 (11)	0.0418 (12)	−0.0014 (8)	0.0047 (9)	0.0046 (9)
O6	0.0440 (13)	0.0198 (9)	0.0305 (10)	−0.0020 (8)	0.0035 (9)	0.0055 (8)
O7	0.0395 (12)	0.0224 (9)	0.0488 (12)	0.0106 (9)	0.0107 (10)	0.0125 (9)
O8	0.0369 (12)	0.0276 (10)	0.0369 (11)	−0.0045 (9)	0.0048 (9)	0.0035 (8)
N1	0.0305 (11)	0.0154 (9)	0.0310 (11)	0.0029 (9)	0.0113 (9)	0.0008 (9)
N2	0.0312 (12)	0.0172 (10)	0.0313 (11)	−0.0004 (9)	0.0121 (10)	0.0011 (9)
N3	0.0305 (12)	0.0187 (10)	0.0282 (11)	−0.0016 (9)	0.0095 (9)	−0.0018 (9)
N4	0.0311 (12)	0.0127 (9)	0.0306 (11)	0.0031 (8)	0.0111 (9)	0.0014 (8)
N5	0.0272 (12)	0.0207 (10)	0.0283 (11)	0.0053 (9)	0.0094 (9)	−0.0017 (8)
N6	0.0314 (13)	0.0229 (11)	0.0427 (14)	0.0025 (10)	0.0208 (11)	0.0070 (10)
N7	0.0299 (12)	0.0211 (10)	0.0254 (11)	0.0028 (9)	0.0069 (9)	−0.0004 (8)
N8	0.0268 (12)	0.0206 (10)	0.0296 (11)	0.0045 (9)	0.0123 (9)	0.0048 (9)
C1	0.0282 (13)	0.0143 (10)	0.0232 (12)	0.0035 (9)	0.0076 (10)	0.0018 (9)
C2	0.0288 (13)	0.0131 (10)	0.0214 (11)	0.0013 (10)	0.0085 (10)	0.0011 (8)
C3	0.0284 (13)	0.0163 (11)	0.0279 (12)	0.0015 (10)	0.0134 (11)	0.0023 (9)
C4	0.0274 (13)	0.0171 (11)	0.0227 (11)	0.0022 (10)	0.0082 (10)	0.0010 (9)
C5	0.0267 (13)	0.0130 (10)	0.0232 (11)	0.0020 (9)	0.0105 (10)	0.0021 (9)
C6	0.0265 (13)	0.0162 (11)	0.0260 (12)	0.0052 (9)	0.0101 (10)	0.0026 (9)

Poly[[µ₄-4-(3,5-dinitropyrazol-4-yl)-3,5-dinitropyrazol-1-ido]caesium] (2) . Geometric parameters (Å, º)

Cs1—O1i	3.071 (2)	O2—N5	1.222 (3)
Cs1—O1ii	3.071 (2)	O3—N6	1.221 (3)
Cs1—O5iii	3.177 (2)	O4—N6	1.225 (3)
Cs1—O5	3.177 (2)	O5—N7	1.229 (3)
Cs1—O3iv	3.351 (3)	O6—N7	1.224 (3)
Cs1—O3v	3.351 (3)	O7—N8	1.230 (3)
Cs1—N3	3.369 (2)	O8—N8	1.225 (3)
Cs1—N3iii	3.369 (2)	N1—N2	1.338 (3)
Cs1—O4iv	3.464 (2)	N1—C1	1.342 (3)
Cs1—O4v	3.464 (2)	N1—H1A	0.8700
Cs1—O8vi	3.514 (2)	N2—C3	1.340 (3)
Cs1—O8vii	3.514 (2)	N3—N4	1.339 (3)
Cs2—O7viii	3.109 (2)	N3—C4	1.340 (3)
Cs2—O7	3.109 (2)	N4—C6	1.346 (3)
Cs2—O5ix	3.159 (2)	N4—H1B	0.8700
Cs2—O5v	3.159 (2)	N5—C1	1.439 (4)
Cs2—O3x	3.297 (2)	N6—C3	1.453 (3)
Cs2—O3ii	3.297 (2)	N7—C4	1.447 (3)
Cs2—O6ix	3.396 (2)	N8—C6	1.432 (3)
Cs2—O6v	3.396 (2)	C1—C2	1.398 (3)
Cs2—N2x	3.401 (2)	C2—C3	1.404 (4)
Cs2—N2ii	3.401 (2)	C2—C5	1.458 (3)
Cs2—O2xi	3.811 (2)	C4—C5	1.396 (4)
Cs2—O2vi	3.811 (2)	C5—C6	1.399 (3)
O1—N5	1.224 (3)
O1i—Cs1—O1ii	112.57 (9)	O5ix—Cs2—N2x	60.69 (6)
O1i—Cs1—O5iii	109.94 (6)	O5v—Cs2—N2x	119.31 (6)
O1ii—Cs1—O5iii	128.30 (6)	O3x—Cs2—N2x	47.39 (5)
O1i—Cs1—O5	128.30 (6)	O3ii—Cs2—N2x	132.61 (5)
O1ii—Cs1—O5	109.94 (6)	O6ix—Cs2—N2x	55.26 (5)
O5iii—Cs1—O5	60.14 (9)	O6v—Cs2—N2x	124.74 (5)
O1i—Cs1—O3iv	101.47 (7)	O7viii—Cs2—N2ii	119.87 (6)
O1ii—Cs1—O3iv	89.92 (7)	O7—Cs2—N2ii	60.13 (6)
O5iii—Cs1—O3iv	53.49 (6)	O5ix—Cs2—N2ii	119.31 (6)
O5—Cs1—O3iv	106.69 (6)	O5v—Cs2—N2ii	60.69 (6)
O1i—Cs1—O3v	89.92 (7)	O3x—Cs2—N2ii	132.61 (5)
O1ii—Cs1—O3v	101.47 (7)	O3ii—Cs2—N2ii	47.39 (5)
O5iii—Cs1—O3v	106.69 (6)	O6ix—Cs2—N2ii	124.74 (5)
O5—Cs1—O3v	53.49 (6)	O6v—Cs2—N2ii	55.26 (5)
O3iv—Cs1—O3v	159.51 (8)	N2x—Cs2—N2ii	180.0
O1i—Cs1—N3	151.61 (7)	O7viii—Cs2—O2xi	46.92 (5)
O1ii—Cs1—N3	61.45 (6)	O7—Cs2—O2xi	133.09 (5)
O5iii—Cs1—N3	92.08 (6)	O5ix—Cs2—O2xi	114.79 (5)
O5—Cs1—N3	48.49 (5)	O5v—Cs2—O2xi	65.21 (5)
O3iv—Cs1—N3	106.11 (6)	O3x—Cs2—O2xi	78.04 (6)
O3v—Cs1—N3	66.04 (6)	O3ii—Cs2—O2xi	101.96 (6)
O1i—Cs1—N3iii	61.45 (6)	O6ix—Cs2—O2xi	100.16 (5)
O1ii—Cs1—N3iii	151.61 (7)	O6v—Cs2—O2xi	79.84 (5)
O5iii—Cs1—N3iii	48.49 (5)	N2x—Cs2—O2xi	54.28 (5)
O5—Cs1—N3iii	92.08 (6)	N2ii—Cs2—O2xi	125.72 (5)
O3iv—Cs1—N3iii	66.03 (6)	O7viii—Cs2—O2vi	133.08 (5)
O3v—Cs1—N3iii	106.11 (6)	O7—Cs2—O2vi	46.91 (5)
N3—Cs1—N3iii	137.57 (8)	O5ix—Cs2—O2vi	65.21 (5)
O1i—Cs1—O4iv	66.05 (7)	O5v—Cs2—O2vi	114.79 (5)
O1ii—Cs1—O4iv	93.97 (7)	O3x—Cs2—O2vi	101.96 (6)
O5iii—Cs1—O4iv	77.60 (6)	O3ii—Cs2—O2vi	78.04 (6)
O5—Cs1—O4iv	137.70 (5)	O6ix—Cs2—O2vi	79.84 (5)
O3iv—Cs1—O4iv	36.92 (6)	O6v—Cs2—O2vi	100.16 (5)
O3v—Cs1—O4iv	155.15 (6)	N2x—Cs2—O2vi	125.72 (5)
N3—Cs1—O4iv	138.81 (6)	N2ii—Cs2—O2vi	54.28 (5)
N3iii—Cs1—O4iv	57.79 (6)	O2xi—Cs2—O2vi	180.00 (6)
O1i—Cs1—O4v	93.97 (7)	N5—O1—Cs1xii	140.2 (2)
O1ii—Cs1—O4v	66.05 (7)	N6—O3—Cs2xii	130.86 (18)
O5iii—Cs1—O4v	137.70 (6)	N6—O3—Cs1xiii	93.91 (18)
O5—Cs1—O4v	77.60 (6)	Cs2xii—O3—Cs1xiii	110.96 (7)
O3iv—Cs1—O4v	155.15 (6)	N6—O4—Cs1xiii	88.50 (16)
O3v—Cs1—O4v	36.92 (6)	N7—O5—Cs2xiv	99.67 (16)
N3—Cs1—O4v	57.79 (6)	N7—O5—Cs1	131.31 (16)
N3iii—Cs1—O4v	138.81 (6)	Cs2xiv—O5—Cs1	119.65 (7)
O4iv—Cs1—O4v	144.69 (7)	N7—O6—Cs2xiv	88.38 (14)
O1i—Cs1—O8vi	140.41 (6)	N8—O7—Cs2	118.85 (17)
O1ii—Cs1—O8vi	48.43 (6)	N8—O8—Cs1vi	127.02 (16)
O5iii—Cs1—O8vi	79.97 (5)	N2—N1—C1	109.8 (2)
O5—Cs1—O8vi	90.40 (5)	N2—N1—H1A	125.1
O3iv—Cs1—O8vi	52.64 (6)	C1—N1—H1A	125.1
O3v—Cs1—O8vi	124.92 (6)	N1—N2—C3	104.9 (2)
N3—Cs1—O8vi	59.05 (6)	N1—N2—Cs2xii	130.12 (15)
N3iii—Cs1—O8vi	116.39 (6)	C3—N2—Cs2xii	121.71 (17)
O4iv—Cs1—O8vi	79.82 (6)	N4—N3—C4	105.1 (2)
O4v—Cs1—O8vi	103.61 (6)	N4—N3—Cs1	128.32 (16)
O1i—Cs1—O8vii	48.43 (6)	C4—N3—Cs1	116.41 (17)
O1ii—Cs1—O8vii	140.41 (6)	N3—N4—C6	109.6 (2)
O5iii—Cs1—O8vii	90.40 (5)	N3—N4—H1B	125.2
O5—Cs1—O8vii	79.97 (5)	C6—N4—H1B	125.2
O3iv—Cs1—O8vii	124.92 (6)	O2—N5—O1	124.3 (3)
O3v—Cs1—O8vii	52.64 (6)	O2—N5—C1	119.1 (2)
N3—Cs1—O8vii	116.39 (6)	O1—N5—C1	116.6 (2)
N3iii—Cs1—O8vii	59.05 (6)	O3—N6—O4	124.1 (3)
O4iv—Cs1—O8vii	103.61 (6)	O3—N6—C3	118.4 (2)
O4v—Cs1—O8vii	79.82 (6)	O4—N6—C3	117.5 (2)
O8vi—Cs1—O8vii	168.92 (7)	O3—N6—Cs1xiii	66.57 (17)
O7viii—Cs2—O7	180.0	O4—N6—Cs1xiii	71.87 (15)
O7viii—Cs2—O5ix	103.32 (6)	C3—N6—Cs1xiii	137.60 (16)
O7—Cs2—O5ix	76.68 (6)	O6—N7—O5	124.3 (2)
O7viii—Cs2—O5v	76.68 (6)	O6—N7—C4	118.3 (2)
O7—Cs2—O5v	103.32 (6)	O5—N7—C4	117.4 (2)
O5ix—Cs2—O5v	180.00 (11)	O6—N7—Cs2xiv	71.61 (14)
O7viii—Cs2—O3x	106.12 (6)	O5—N7—Cs2xiv	60.53 (14)
O7—Cs2—O3x	73.88 (6)	C4—N7—Cs2xiv	149.11 (16)
O5ix—Cs2—O3x	54.16 (6)	O8—N8—O7	124.3 (2)
O5v—Cs2—O3x	125.84 (6)	O8—N8—C6	118.5 (2)
O7viii—Cs2—O3ii	73.88 (6)	O7—N8—C6	117.1 (2)
O7—Cs2—O3ii	106.12 (6)	N1—C1—C2	111.4 (2)
O5ix—Cs2—O3ii	125.84 (6)	N1—C1—N5	119.1 (2)
O5v—Cs2—O3ii	54.16 (6)	C2—C1—N5	129.5 (2)
O3x—Cs2—O3ii	180.00 (10)	C1—C2—C3	99.5 (2)
O7viii—Cs2—O6ix	68.69 (6)	C1—C2—C5	130.2 (3)
O7—Cs2—O6ix	111.31 (6)	C3—C2—C5	130.2 (2)
O5ix—Cs2—O6ix	38.43 (5)	N2—C3—C2	114.3 (2)
O5v—Cs2—O6ix	141.57 (5)	N2—C3—N6	117.7 (2)
O3x—Cs2—O6ix	80.81 (5)	C2—C3—N6	127.8 (2)
O3ii—Cs2—O6ix	99.19 (5)	N3—C4—C5	114.3 (2)
O7viii—Cs2—O6v	111.31 (6)	N3—C4—N7	118.3 (2)
O7—Cs2—O6v	68.69 (6)	C5—C4—N7	127.3 (2)
O5ix—Cs2—O6v	141.57 (5)	C4—C5—C6	99.9 (2)
O5v—Cs2—O6v	38.43 (5)	C4—C5—C2	129.6 (2)
O3x—Cs2—O6v	99.19 (5)	C6—C5—C2	130.6 (2)
O3ii—Cs2—O6v	80.81 (5)	N4—C6—C5	111.1 (2)
O6ix—Cs2—O6v	180.00 (9)	N4—C6—N8	119.0 (2)
O7viii—Cs2—N2x	60.13 (6)	C5—C6—N8	129.8 (2)
O7—Cs2—N2x	119.87 (6)
C1—N1—N2—C3	−0.7 (3)	C1—C2—C3—N2	−0.1 (3)
C1—N1—N2—Cs2xii	158.78 (16)	C5—C2—C3—N2	−178.3 (2)
C4—N3—N4—C6	−0.6 (3)	C1—C2—C3—N6	175.2 (2)
Cs1—N3—N4—C6	142.57 (18)	C5—C2—C3—N6	−3.1 (4)
Cs1xii—O1—N5—O2	53.4 (5)	O3—N6—C3—N2	−22.2 (4)
Cs1xii—O1—N5—C1	−127.5 (3)	O4—N6—C3—N2	156.2 (2)
Cs2xii—O3—N6—O4	−167.5 (2)	Cs1xiii—N6—C3—N2	63.3 (3)
Cs1xiii—O3—N6—O4	−45.3 (3)	O3—N6—C3—C2	162.7 (3)
Cs2xii—O3—N6—C3	10.7 (4)	O4—N6—C3—C2	−18.9 (4)
Cs1xiii—O3—N6—C3	132.9 (2)	Cs1xiii—N6—C3—C2	−111.8 (3)
Cs2xii—O3—N6—Cs1xiii	−122.2 (2)	N4—N3—C4—C5	0.4 (3)
Cs1xiii—O4—N6—O3	43.4 (3)	Cs1—N3—C4—C5	−147.90 (19)
Cs1xiii—O4—N6—C3	−134.9 (2)	N4—N3—C4—N7	−178.0 (2)
Cs2xiv—O6—N7—O5	31.4 (3)	Cs1—N3—C4—N7	33.7 (3)
Cs2xiv—O6—N7—C4	−148.0 (2)	O6—N7—C4—N3	155.1 (3)
Cs2xiv—O5—N7—O6	−34.6 (3)	O5—N7—C4—N3	−24.4 (4)
Cs1—O5—N7—O6	−179.42 (19)	Cs2xiv—N7—C4—N3	53.4 (4)
Cs2xiv—O5—N7—C4	144.81 (19)	O6—N7—C4—C5	−23.1 (4)
Cs1—O5—N7—C4	0.0 (4)	O5—N7—C4—C5	157.4 (3)
Cs1—O5—N7—Cs2xiv	−144.8 (2)	Cs2xiv—N7—C4—C5	−124.8 (3)
Cs1vi—O8—N8—O7	26.7 (4)	N3—C4—C5—C6	−0.1 (3)
Cs1vi—O8—N8—C6	−152.15 (18)	N7—C4—C5—C6	178.2 (3)
Cs2—O7—N8—O8	66.2 (3)	N3—C4—C5—C2	179.4 (3)
Cs2—O7—N8—C6	−114.9 (2)	N7—C4—C5—C2	−2.3 (5)
N2—N1—C1—C2	0.7 (3)	C1—C2—C5—C4	−43.6 (4)
N2—N1—C1—N5	−178.4 (2)	C3—C2—C5—C4	134.1 (3)
O2—N5—C1—N1	169.4 (2)	C1—C2—C5—C6	135.7 (3)
O1—N5—C1—N1	−9.8 (4)	C3—C2—C5—C6	−46.5 (4)
O2—N5—C1—C2	−9.5 (4)	N3—N4—C6—C5	0.5 (3)
O1—N5—C1—C2	171.4 (3)	N3—N4—C6—N8	−176.5 (2)
N1—C1—C2—C3	−0.4 (3)	C4—C5—C6—N4	−0.3 (3)
N5—C1—C2—C3	178.5 (2)	C2—C5—C6—N4	−179.8 (3)
N1—C1—C2—C5	177.9 (2)	C4—C5—C6—N8	176.4 (3)
N5—C1—C2—C5	−3.2 (5)	C2—C5—C6—N8	−3.1 (5)
N1—N2—C3—C2	0.5 (3)	O8—N8—C6—N4	175.1 (2)
Cs2xii—N2—C3—C2	−161.16 (16)	O7—N8—C6—N4	−3.9 (4)
N1—N2—C3—N6	−175.3 (2)	O8—N8—C6—C5	−1.4 (4)
Cs2xii—N2—C3—N6	23.1 (3)	O7—N8—C6—C5	179.6 (3)

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

Poly[[µ₄-4-(3,5-dinitropyrazol-4-yl)-3,5-dinitropyrazol-1-ido]caesium] (2) . Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N4xii	0.87	1.99	2.832 (3)	162
N4—H1B···N1ii	0.87	1.99	2.832 (3)	163

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

Funding Statement

This work was funded by Ministry of Education and Science of Ukraine grant 19BF037-05.