Two different anionic manganese(II) coordination polymers constructed through dicyanamide coordination bridges

In order to explore new metal coordination polymers and to search for new types of ferroelectrics among hybrid coordination polymers, two manganese dicyanamide complexes, poly[tetra­methyl­ammonium [di-μ₃-dicyanamido-κ⁶N¹:N³:N⁵-tri-μ₂-dicyanamido-κ⁶N¹:N⁵-dimanganese(II)]], {[(CH₃)₄N][Mn₂(NCNCN)₅]}_n, (I), and catena-poly[bis­(butyl­tri­phenyl­phospho­nium) [[(dicyanamido-κN¹)manganese(II)]-di-μ₂-dicyanamido-κ⁴N¹:N⁵]], {[(C₄H₉)(C₆H₅)₃P]₂[Mn(NCNCN)₄]}_n, (II), were synthesized in aqueous solution. In (I), one Mn^II cation is octa­hedrally coordinated by six nitrile N atoms from six anionic dicyanamide (dca) ligands, while the second Mn^II cation is coordinated by four nitrile N atoms and two amide N atoms from six anionic dca ligands. Neighbouring Mn^II cations are linked together by μ-1,5- and μ-1,3,5-bridging dca anions to form a three-dimensional polymeric structure. The anionic framework exhibits a solvent-accessible void of 289.8 ų, amounting to 28.0% of the total unit-cell volume. Each of the cavities in the network is occupied by only one tetra­methyl­ammonium cation. In (II), each Mn^II cation is octa­hedrally coordinated by six nitrile N atoms from six dca ligands. Neighbouring Mn^II cations are linked together by double dca bridges to form a one-dimensional polymeric chain, and C—H...N hydrogen-bonding inter­actions are involved in the formation of the one-dimensional layer structure.

S1. Introduction

Much attention has been concentrated on the crystal engineering of new dielectric and ferroelectric materials in recent years, owing to their novel structural characteristics and potential applications, for instance as filters, capacitors, resonators, switchable nonlinear optical devices or solid-state transducer components in microwave communication systems (Vanderah, 2002; Fu et al., 2008; Ye et al., 2013; Shi et al., 2015). In the search for potential ferroelectric materials, molecular-based one-, two- and three-dimensional metal organic–inorganic compounds have been of inter­est as they often display solid–solid phase transitions induced by a variation in temperature. Many reports have been devoted to the formation of infinite polymeric frameworks through N-donor bridging ligands (Olenyuk et al., 1999; Rosi et al., 2003; Li, 2015). In contrast to the cyanamide ligands [N(CN)Y]^- [Y = Ph₂P(S), Ph₂P(NCN) or NO₂], the pseudohalide ligand dicyanamide [dca, N(CN)₂^-] is a remarkably versatile building block for the construction of metal–organic architectures since it may act as a mono-, bi- and tridentate ligand, yielding a variety of novel structures (Sun et al., 2001).

A notable feature of metal–dca coordination polymers is the ability of cations to template anionic [M(dca)₃]^- networks (Biswas et al., 2006). The prime cases of previously reported three-dimensional metal–dca networks are neutral binary systems. The series MX₂ with X = [N(CN)₂]^- (M = Cr²⁺, Mn²⁺, Co²⁺, Ni²⁺ or Cu²⁺ ) and related complexes have attracted increased inter­est because of their rutile-like structures containing chains of doubly-bridged metal atoms with M(NCNCN)M units (Li & Wang, 2014). According to previous reports, the pseudohalide ligand dicyanamide plays an instructive role in building coordination polymers. In order to explore new metal coordination polymers and to search for new types of ferroelectrics among hybrid coordination polymers, we report here the use of tetra­methyl­ammonium and butyl­tri­phenyl­phospho­nium cations as templates for the formation of two different coordination polymers, namely {(Me₄N)[Mn₂(dca)₅]}_n, (I), and {(BuPh₃P)₂[Mn(dca)₄]}_n, (II), which exhibit inter­esting structural features.

S2. Experimental

S2.1. Synthesis and crystallization

A solution of sodium dicyanamide (0.801 g, 9 mmol) in water was added to a solution of tetra­methyl­ammonium chloride (0.329 g, 3 mmol) in water. Mn(NO₃)₂·4H₂O (1.073 g, 3 mmol) was then added, affording a colourless solution. Upon standing at room temperature for several days, suitable colourless single crystals of (I) were obtained by slow solvent evaporation.

For the synthesis of (II), n-butyl­tri­phenyl­phospho­nium bromide was used instead of tetra­methyl­ammonium chloride. Using the same method as for the preparation of (I), suitable colourless single crystals of (II) were obtained.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were refined isotropically. H atoms on C atoms were included in calculated positions and were refined as riding, with C—H = 0.93 (aromatic), 0.96 (methyl) or 0.97 Å (methyl­ene), and with U_iso(H) = 1.5UU_eq(C) for methyl H atoms or 1.2UU_eq(C) otherwise.

S3. Results and discussion

The asymmetric unit of complex (I) contains two independent Mn^II cations, five anionic dicyanamide (dca) ligands, complemented by a tetra­methyl­ammonium counter-ion (Fig. 1). As shown in Fig. 1, there are two unique o­cta­hedrally coordinated Mn^II cations with similar coordination models. The central Mn1 cation is six-coordinated by six nitrile N atoms from six anionic dca ligands, adopting a distorted o­cta­hedral coordination geometry, with the N1, N3, N4 and N6 atoms in the basal plane and atoms N2 and N5 in apical positions. The Mn2 cation also adopts a distorted o­cta­hedral coordination geometry, with the N7, N8, N11ⁱ and N15ⁱⁱ atoms in the basal plane, and atoms N9ⁱⁱ and N13ⁱⁱⁱ in the apical position (symmetry codes are as in Table 2), and is surrounded by four nitrile N atoms from four anionic dca ligands and two amide N atoms from dca ligands. Each Mn^II cation is joined to neighbouring Mn^II cations through µ-1,5- and µ-1,3,5-bridging dicyanamide ligands. The Mn—N(nitrile) bond lengths range from 2.152 (2) to 2.389 (2) Å and the Mn—N(amide) bond lengths vary between 2.397 (2) and 2.421 (2) Å (Table 2). There are two sorts of angles around each Mn^II centre, namely orthogonal cis angles [81.61 (8)–98.47 (9)°] and linear trans angles [167.69 (8)–174.12 (8)°]. The Mn—N(nitrile) [2.203 (2)–2.389 (2) Å] bond lengths of the µ-1,3,5-bridging dicyanamide ligands are significantly longer than those of the µ-1,5-bridging dicyanamide ligands [2.152 (2)–2.198 (2) Å]. And the Mn—N(amide) bond lengths of the µ-1,3,5-bridging dicyanamide ligands are consistent with those of other reported manganese–dicyanamide compounds (Luo et al., 2005). The N4—C5, C5—N10 and N11—C6 bond lengths (Table 2) indicate triple- and single-bond character, as is typical for bridging [N(CN)₂]^- ligands. All bond lengths and angles within the dicyanamide ligands are almost typical of the M—N···C—N—C···N—M and M—N···C—N(Mn)—C···N—M bridging modes.

Compound (I) is a new coordination polymer in which both of the six-coordinated Mn^II centres adopt a distorted o­cta­hedral coordination geometry. It displays a novel coordination architecture compared with the similar compound, [Mn(dmpz){N(CN)₂}₂]₂, (III) (dmpz is 3,5-di­methyl­pyrazole; Luo et al., 2005), in which the central Mn1 cation is coordinated by four dicyanamide nitrile N atoms and two atoms of dmpz molecules, rather than six nitrile N atoms from six anionic dca ligands, as for atom Mn1 in (I). In (I), the overall crystal structure motif exhibits linear M—dca—M bridging mode, which consists of µ-1,5- and µ-1,3,5-bridging dicyanamide anions, forming a three-dimensional anionic network (Fig. 3a). This is also different from what was found in our previous work. In [(CH₃)₄P][Cd(NCNCN)₂Cl], one type of dca ligand is involved in the formation of [Cd(dca)Cl]₂ building blocks and the other links these building blocks into a three-dimensional structure (Li & Wang, 2014). The amide N atom of the µ-1,3,5-bridging dicyanamide anions connects adjacent the Mn^II cations into an eight-membered [Mn₂(dca)] ring; meanwhile, the amide N atom of the µ-1,3,5-bridging dicyanamide ligands and the nitrile N atom of µ-1,5-bridging dicyanamide ligands are bonded to adjacent Mn^II cations, forming a large 20-membered [Mn₄(dca)₄] ring (Fig. 2). The Mn···Mn distance across the µ-1,3,5-bridging dca is 8.533 (3) Å, while the shortest Mn···Mn contact across the µ-1,3-bridging dca ligand is 5.716 (3) Å. This phenomenon in (I) is different from the two-dimensional compound [Mn(dca)₂(pydz)]_n (Wriedt & Näther, 2011), where the metal atoms are connected in one direction by double M(dca)₂M bridges and in the other by the amide N atom of the µ-1,3,5-bridging dca ligand, forming a two-dimensional layer structure.

It should be pointed out that the three-dimensional anionic framework in (I) exhibits a void space of 289.8 ų, which amounts to 28.0% of the unit-cell volume. Additionally, each of the cavities in (I) accommodates only one tetra­methyl­ammonium cation, but the orientations of the cations in adjacent cages are different (Fig. 3b). The distances of between the two cations is 8.691 (4) Å. This marks a difference with regard to the related (Ph₄E)[Mn(dca)₃] (E = P or As) structures, where two-dimensional anionic [Mn(dca)₃]^- sheets are separated by layers of Ph₄E⁺ cations (van der Werff et al., 2001). In addition, in these compounds, the cations lie in pairs within cavities in the anionic network. The tetra­methyl­ammonium cations do not participate in any significant supra­molecular inter­actions, though they are obviously important for stabilizing the structure.

The asymmetric unit of complex (II) contains half Mn^II cation, four half anionic dicyanamide (dca) ligands, complemented by a noncoordinating n-butyl­tri­phenyl­phospho­nium [(n-butyl)PPh₃] counter-ion (Fig. 4). As shown in Fig. 4, the central Mn^II cation is six-coordinated by six terminal N atoms from six different dca ligands, four of which are bridging, adopting a slightly distorted o­cta­hedral coordinated geometry, with the N1, N1ⁱ, N3 and N3ⁱ atoms in the basal plane, and the N4 and N4ⁱ atoms in the apical position [symmetry code: (i) -x+1, -y+2, -z]. Each Mn^II cation is connected to two neighbouring Mn^II cations through bridging double dca ligands. The Mn—N bond lengths (Table 2) and cis-N—Mn—N angles range from 87.17 (12) to 92.83 (12)°, with a trans angle of 180.0 (2)°, which are all in good agreement with values found in other Mn^II complexes with a six-coordinated geometry (van der Werff et al., 2001). All bond lengths and angles within the n-butyl­tri­phenyl­phospho­nium ligand are typical and the benzene ring is strictly planar.

In contrast with the structure of (I), in (II), double dca bridges exist between adjacent Mn^II cations to give a chain structure, with an Mn··· Mn distance of 7.6050 (15) Å. In addition, the one-dimensional anionic framework is filled by n-butyl­tri­phenyl­phospho­nium cations through electrostatic and hydrogen-bonding inter­actions (C19—H19B···N6 and C19—H19A···N5; Table 3). Inter­molecular hydrogen-bonding inter­actions between the cations and the bridging thio­cyanate ligands further stabilize the one-dimensional layer structure (Fig. 5).

Our original inter­est in (I) and (II) lay mainly in their potential as phase-transition materials (Ye et al., 2013; Fu et al., 2013; Shi et al., 2014; Liao et al., 2014). The variable-temperature dielectric response, especially in the relatively high frequency range, is treated as an effective indicator of a structural phase transition. However, measurement of theirs dielectric properties with varying temperature did not observe dielectric anomalies within the temperature range 90–380 K. This reveals that the two compounds might not undergo a distinct structural phase transition within this temperature range and so both of them are not ferroelectric materials like those reported earlier (Ye et al., 2009; Fu et al., 2008). Further phase-transition materials still need to be sought and explored, and other related materials are currently being investigated for dielectric properties and ferroelectric activity.

Computing details

For both compounds, data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The coordination environment of atoms Mn1 and Mn2 in (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms have been omitted for clarity. [Symmetry codes: (i) -x+1, -y+2, -z+2; (ii) -x+1, -y+1,-z+2; (iii) -x, -y+2, -z+2; (iv) -x, -y+2, -z+1.]
	Fig. 2. The fragment for a single coordination net of (I) projected onto the ac plane.
	Fig. 3. (a) The crystal packing of (I). All H atoms have been omitted for clarity. Note the corrugation of the anionic network. (b) Two cations contained inside anionic cavities in the structure of (I).
	Fig. 4. The structural unit of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms have been omitted for clarity. [Symmetry codes: (i) -x+1, -y+2, -z; (ii) x, y+1, z; (iii) x, y-1, z.]
	Fig. 5. The crystal packing of (II), showing the hydrogen-bonding interactions (dashed lines) among the cationic ligands and the coordination polymer.

(1) Poly[tetramethylammonium [di-µ₃-dicyanamido-κ⁶N¹:N³:N⁵-tri-µ₂-dicyanamido-κ⁶N¹:N⁵-dimanganese(II)]]

Crystal data

(C4H12N)[Mn2(C2N3)5]	Z = 2
Mr = 514.28	F(000) = 516
Triclinic, P1	Dx = 1.650 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.368 (2) Å	Cell parameters from 4723 reflections
b = 10.377 (2) Å	θ = 3.5–27.5°
c = 11.898 (2) Å	µ = 1.26 mm^−1
α = 65.64 (3)°	T = 293 K
β = 82.28 (3)°	Block, colourless
γ = 62.83 (3)°	0.30 × 0.25 × 0.20 mm
V = 1035.1 (3) Å^3

Data collection

Rigaku SCXmini diffractometer	4245 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
Graphite monochromator	θmax = 27.5°, θmin = 3.5°
ω scans	h = −13→13
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −13→13
Tmin = 0.704, Tmax = 0.787	l = −15→15
10736 measured reflections	3 standard reflections every 180 reflections
4723 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.094	w = 1/[σ^2(Fo^2) + (0.0377P)^2 + 0.8558P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
4723 reflections	Δρmax = 0.61 e Å^−3
289 parameters	Δρmin = −0.51 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0819 (12)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Mn2	0.15430 (3)	0.77945 (4)	0.73446 (3)	0.02088 (9)
Mn1	0.45551 (3)	1.14431 (4)	0.73319 (3)	0.02105 (9)
N1	0.3662 (2)	1.0750 (3)	0.61795 (19)	0.0368 (5)
N3	0.2807 (2)	1.4121 (2)	0.62898 (19)	0.0355 (5)
N4	0.5090 (2)	1.2376 (3)	0.84650 (19)	0.0381 (5)
N6	0.6323 (2)	0.9083 (2)	0.8239 (2)	0.0379 (5)
N7	0.1864 (2)	1.0001 (2)	0.58237 (17)	0.0283 (4)
N8	0.0182 (2)	1.1541 (3)	0.39690 (19)	0.0373 (5)
N11	0.6630 (2)	1.2544 (2)	1.17046 (19)	0.0349 (5)
N15	0.8366 (2)	0.4475 (2)	1.14708 (18)	0.0309 (4)
N13	0.0045 (2)	1.0823 (3)	1.1730 (2)	0.0387 (5)
N9	0.6950 (2)	1.3521 (2)	0.39593 (17)	0.0303 (4)
N10	0.5053 (3)	1.3484 (3)	0.9922 (2)	0.0408 (5)
N5	0.2942 (3)	1.1001 (3)	0.8620 (2)	0.0405 (5)
N2	0.5898 (2)	1.2214 (3)	0.5791 (2)	0.0378 (5)
N12	0.1520 (2)	0.9928 (3)	1.0187 (2)	0.0395 (5)
N14	0.8310 (2)	0.6742 (2)	0.9648 (2)	0.0400 (5)
C1	0.2814 (2)	1.0441 (2)	0.59740 (19)	0.0251 (4)
C2	0.1000 (2)	1.0866 (2)	0.4808 (2)	0.0254 (4)
C6	0.5945 (2)	1.2896 (2)	1.0857 (2)	0.0246 (4)
C5	0.5144 (2)	1.2812 (3)	0.9192 (2)	0.0274 (5)
C10	0.8246 (2)	0.5586 (3)	1.0610 (2)	0.0250 (4)
C3	0.6385 (2)	1.2853 (3)	0.4957 (2)	0.0260 (4)
C9	0.7197 (3)	0.7957 (3)	0.8947 (2)	0.0283 (5)
C8	0.0765 (2)	1.0476 (3)	1.0984 (2)	0.0278 (5)
C4	0.2941 (2)	1.5225 (3)	0.61405 (19)	0.0257 (4)
C7	0.2257 (2)	1.0559 (3)	0.9383 (2)	0.0291 (5)
N16	0.1781 (2)	0.5460 (2)	0.26852 (19)	0.0367 (5)
C11	0.1565 (4)	0.6144 (4)	0.1308 (3)	0.0633 (9)
H11A	0.2212	0.5365	0.1000	0.095*
H11B	0.1765	0.7045	0.0962	0.095*
H11C	0.0579	0.6464	0.1077	0.095*
C14	0.1499 (12)	0.4125 (9)	0.3200 (5)	0.208 (5)
H14A	0.1640	0.3689	0.4085	0.312*
H14B	0.2150	0.3346	0.2893	0.312*
H14C	0.0514	0.4435	0.2972	0.312*
C13	0.0815 (10)	0.6616 (7)	0.3168 (5)	0.177 (4)
H13A	0.0965	0.6161	0.4053	0.265*
H13B	−0.0174	0.6937	0.2944	0.265*
H13C	0.1011	0.7519	0.2829	0.265*
C12	0.3210 (6)	0.5052 (12)	0.3027 (4)	0.195 (5)
H12A	0.3346	0.4611	0.3912	0.293*
H12B	0.3369	0.5978	0.2685	0.293*
H12C	0.3888	0.4288	0.2717	0.293*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn2	0.02375 (17)	0.02298 (17)	0.01556 (16)	−0.01156 (13)	−0.00151 (12)	−0.00519 (13)
Mn1	0.02544 (17)	0.02405 (17)	0.01714 (16)	−0.01521 (13)	0.00159 (12)	−0.00659 (13)
N1	0.0471 (12)	0.0424 (12)	0.0319 (11)	−0.0306 (10)	−0.0054 (9)	−0.0103 (9)
N3	0.0472 (12)	0.0294 (10)	0.0321 (11)	−0.0192 (9)	0.0043 (9)	−0.0121 (9)
N4	0.0436 (12)	0.0432 (12)	0.0328 (11)	−0.0179 (10)	−0.0065 (9)	−0.0188 (10)
N6	0.0393 (12)	0.0279 (10)	0.0340 (11)	−0.0121 (9)	−0.0050 (9)	−0.0019 (9)
N7	0.0341 (10)	0.0294 (10)	0.0226 (9)	−0.0200 (8)	−0.0089 (8)	−0.0015 (8)
N8	0.0412 (12)	0.0371 (11)	0.0306 (11)	−0.0242 (10)	−0.0135 (9)	0.0017 (9)
N11	0.0404 (11)	0.0342 (11)	0.0315 (11)	−0.0175 (9)	−0.0101 (9)	−0.0097 (9)
N15	0.0302 (10)	0.0258 (10)	0.0273 (10)	−0.0105 (8)	0.0005 (8)	−0.0040 (8)
N13	0.0419 (12)	0.0427 (12)	0.0379 (12)	−0.0227 (10)	0.0155 (10)	−0.0211 (10)
N9	0.0429 (11)	0.0301 (10)	0.0246 (10)	−0.0228 (9)	0.0126 (8)	−0.0123 (8)
N10	0.0468 (13)	0.0333 (11)	0.0398 (12)	−0.0075 (9)	−0.0209 (10)	−0.0169 (10)
N5	0.0467 (13)	0.0468 (13)	0.0352 (12)	−0.0282 (11)	0.0165 (10)	−0.0185 (10)
N2	0.0439 (12)	0.0400 (12)	0.0342 (11)	−0.0261 (10)	0.0152 (10)	−0.0144 (10)
N12	0.0435 (12)	0.0463 (13)	0.0501 (13)	−0.0327 (11)	0.0265 (10)	−0.0309 (11)
N14	0.0285 (10)	0.0280 (10)	0.0403 (12)	−0.0110 (8)	0.0011 (9)	0.0060 (9)
C1	0.0328 (11)	0.0243 (10)	0.0191 (10)	−0.0146 (9)	−0.0021 (8)	−0.0062 (8)
C2	0.0302 (11)	0.0247 (10)	0.0250 (11)	−0.0181 (9)	−0.0005 (9)	−0.0058 (9)
C6	0.0272 (10)	0.0238 (10)	0.0254 (11)	−0.0133 (9)	−0.0006 (9)	−0.0093 (9)
C5	0.0254 (11)	0.0276 (11)	0.0264 (11)	−0.0121 (9)	−0.0056 (9)	−0.0059 (9)
C10	0.0231 (10)	0.0253 (11)	0.0258 (11)	−0.0106 (8)	0.0015 (8)	−0.0099 (9)
C3	0.0263 (11)	0.0272 (11)	0.0269 (11)	−0.0134 (9)	0.0052 (9)	−0.0122 (9)
C9	0.0343 (12)	0.0265 (11)	0.0266 (11)	−0.0182 (10)	0.0062 (9)	−0.0088 (9)
C8	0.0288 (11)	0.0262 (11)	0.0304 (12)	−0.0162 (9)	0.0046 (9)	−0.0093 (9)
C4	0.0295 (11)	0.0280 (11)	0.0184 (10)	−0.0131 (9)	0.0052 (8)	−0.0089 (9)
C7	0.0282 (11)	0.0322 (12)	0.0310 (12)	−0.0140 (10)	0.0061 (9)	−0.0166 (10)
N16	0.0452 (12)	0.0358 (11)	0.0289 (11)	−0.0233 (10)	−0.0032 (9)	−0.0050 (9)
C11	0.094 (3)	0.063 (2)	0.0319 (15)	−0.041 (2)	−0.0114 (16)	−0.0069 (15)
C14	0.460 (15)	0.194 (7)	0.065 (3)	−0.268 (10)	−0.018 (6)	0.014 (4)
C13	0.254 (9)	0.092 (4)	0.064 (3)	0.027 (5)	−0.018 (4)	−0.032 (3)
C12	0.071 (3)	0.437 (14)	0.055 (3)	−0.116 (6)	0.012 (2)	−0.076 (5)

Geometric parameters (Å, º)

Mn2—N11^i	2.152 (2)	N9—C3	1.318 (3)
Mn2—N15^ii	2.154 (2)	N9—Mn2^v	2.421 (2)
Mn2—N13^iii	2.154 (2)	N10—C6	1.291 (3)
Mn2—N8^iv	2.203 (2)	N10—C5	1.291 (3)
Mn2—N7	2.397 (2)	N5—C7	1.149 (3)
Mn2—N9^v	2.421 (2)	N2—C3	1.144 (3)
Mn1—N6	2.185 (2)	N12—C7	1.293 (3)
Mn1—N5	2.188 (2)	N12—C8	1.293 (3)
Mn1—N4	2.198 (2)	N14—C10	1.293 (3)
Mn1—N1	2.240 (2)	N14—C9	1.296 (3)
Mn1—N2	2.250 (2)	C4—N9^vi	1.314 (3)
Mn1—N3	2.389 (2)	N16—C12	1.409 (5)
N1—C1	1.148 (3)	N16—C14	1.414 (5)
N3—C4	1.155 (3)	N16—C13	1.446 (6)
N4—C5	1.147 (3)	N16—C11	1.494 (3)
N6—C9	1.150 (3)	C11—H11A	0.9600
N7—C2	1.315 (3)	C11—H11B	0.9600
N7—C1	1.317 (3)	C11—H11C	0.9600
N8—C2	1.146 (3)	C14—H14A	0.9600
N8—Mn2^iv	2.203 (2)	C14—H14B	0.9600
N11—C6	1.143 (3)	C14—H14C	0.9600
N11—Mn2^i	2.152 (2)	C13—H13A	0.9600
N15—C10	1.150 (3)	C13—H13B	0.9600
N15—Mn2^ii	2.154 (2)	C13—H13C	0.9600
N13—C8	1.147 (3)	C12—H12A	0.9600
N13—Mn2^iii	2.154 (2)	C12—H12B	0.9600
N9—C4^vi	1.314 (3)	C12—H12C	0.9600
N11^i—Mn2—N15^ii	94.74 (9)	C7—N5—Mn1	170.1 (2)
N11^i—Mn2—N13^iii	94.13 (9)	C3—N2—Mn1	168.4 (2)
N15^ii—Mn2—N13^iii	98.47 (9)	C7—N12—C8	124.2 (2)
N11^i—Mn2—N8^iv	167.94 (8)	C10—N14—C9	124.9 (2)
N15^ii—Mn2—N8^iv	95.82 (8)	N1—C1—N7	175.6 (2)
N13^iii—Mn2—N8^iv	90.08 (9)	N8—C2—N7	174.0 (2)
N11^i—Mn2—N7	83.03 (8)	N11—C6—N10	171.6 (3)
N15^ii—Mn2—N7	167.69 (8)	N4—C5—N10	172.1 (3)
N13^iii—Mn2—N7	93.77 (8)	N15—C10—N14	171.9 (2)
N8^iv—Mn2—N7	85.42 (8)	N2—C3—N9	175.9 (2)
N11^i—Mn2—N9^v	93.46 (8)	N6—C9—N14	172.2 (3)
N15^ii—Mn2—N9^v	85.32 (7)	N13—C8—N12	171.9 (2)
N13^iii—Mn2—N9^v	171.20 (8)	N3—C4—N9^vi	176.1 (2)
N8^iv—Mn2—N9^v	81.61 (8)	N5—C7—N12	172.7 (3)
N7—Mn2—N9^v	82.74 (7)	C12—N16—C14	110.9 (6)
N6—Mn1—N5	95.02 (9)	C12—N16—C13	106.9 (5)
N6—Mn1—N4	92.71 (9)	C14—N16—C13	109.2 (6)
N5—Mn1—N4	89.91 (9)	C12—N16—C11	109.7 (3)
N6—Mn1—N1	94.57 (9)	C14—N16—C11	109.7 (3)
N5—Mn1—N1	84.82 (9)	C13—N16—C11	110.4 (3)
N4—Mn1—N1	171.36 (8)	N16—C11—H11A	109.5
N6—Mn1—N2	93.68 (9)	N16—C11—H11B	109.5
N5—Mn1—N2	170.61 (9)	H11A—C11—H11B	109.5
N4—Mn1—N2	93.21 (9)	N16—C11—H11C	109.5
N1—Mn1—N2	90.97 (8)	H11A—C11—H11C	109.5
N6—Mn1—N3	174.12 (8)	H11B—C11—H11C	109.5
N5—Mn1—N3	89.89 (9)	N16—C14—H14A	109.5
N4—Mn1—N3	84.04 (8)	N16—C14—H14B	109.5
N1—Mn1—N3	89.10 (8)	H14A—C14—H14B	109.5
N2—Mn1—N3	81.64 (8)	N16—C14—H14C	109.5
C1—N1—Mn1	151.2 (2)	H14A—C14—H14C	109.5
C4—N3—Mn1	125.72 (19)	H14B—C14—H14C	109.5
C5—N4—Mn1	166.1 (2)	N16—C13—H13A	109.5
C9—N6—Mn1	163.5 (2)	N16—C13—H13B	109.5
C2—N7—C1	118.04 (19)	H13A—C13—H13B	109.5
C2—N7—Mn2	118.34 (14)	N16—C13—H13C	109.5
C1—N7—Mn2	123.55 (14)	H13A—C13—H13C	109.5
C2—N8—Mn2^iv	162.10 (18)	H13B—C13—H13C	109.5
C6—N11—Mn2^i	155.2 (2)	N16—C12—H12A	109.5
C10—N15—Mn2^ii	162.25 (19)	N16—C12—H12B	109.5
C8—N13—Mn2^iii	161.7 (2)	H12A—C12—H12B	109.5
C4^vi—N9—C3	117.33 (19)	N16—C12—H12C	109.5
C4^vi—N9—Mn2^v	115.55 (14)	H12A—C12—H12C	109.5
C3—N9—Mn2^v	124.20 (15)	H12B—C12—H12C	109.5
C6—N10—C5	125.6 (2)
N6—Mn1—N1—C1	103.6 (4)	N4—Mn1—N5—C7	−90.2 (12)
N5—Mn1—N1—C1	9.0 (4)	N1—Mn1—N5—C7	96.6 (12)
N4—Mn1—N1—C1	−43.7 (8)	N2—Mn1—N5—C7	160.3 (10)
N2—Mn1—N1—C1	−162.6 (4)	N3—Mn1—N5—C7	−174.3 (12)
N3—Mn1—N1—C1	−81.0 (4)	N6—Mn1—N2—C3	−171.4 (10)
N6—Mn1—N3—C4	−23.7 (9)	N5—Mn1—N2—C3	30.7 (13)
N5—Mn1—N3—C4	122.8 (2)	N4—Mn1—N2—C3	−78.5 (10)
N4—Mn1—N3—C4	32.9 (2)	N1—Mn1—N2—C3	93.9 (10)
N1—Mn1—N3—C4	−152.4 (2)	N3—Mn1—N2—C3	5.0 (10)
N2—Mn1—N3—C4	−61.3 (2)	Mn1—N1—C1—N7	−56 (4)
N6—Mn1—N4—C5	−98.8 (8)	C2—N7—C1—N1	173 (3)
N5—Mn1—N4—C5	−3.8 (8)	Mn2—N7—C1—N1	−4 (4)
N1—Mn1—N4—C5	48.5 (11)	Mn2^iv—N8—C2—N7	−14 (3)
N2—Mn1—N4—C5	167.3 (8)	C1—N7—C2—N8	−171 (2)
N3—Mn1—N4—C5	86.1 (8)	Mn2—N7—C2—N8	6 (3)
N5—Mn1—N6—C9	−63.0 (7)	Mn2^i—N11—C6—N10	−101.0 (18)
N4—Mn1—N6—C9	27.1 (7)	C5—N10—C6—N11	179 (100)
N1—Mn1—N6—C9	−148.2 (7)	Mn1—N4—C5—N10	−80 (2)
N2—Mn1—N6—C9	120.5 (7)	C6—N10—C5—N4	−174.9 (18)
N3—Mn1—N6—C9	83.4 (11)	Mn2^ii—N15—C10—N14	−98.7 (18)
N11^i—Mn2—N7—C2	178.26 (19)	C9—N14—C10—N15	173.8 (17)
N15^ii—Mn2—N7—C2	98.1 (4)	Mn1—N2—C3—N9	−119 (3)
N13^iii—Mn2—N7—C2	−88.03 (19)	C4^vi—N9—C3—N2	174 (4)
N8^iv—Mn2—N7—C2	1.75 (18)	Mn2^v—N9—C3—N2	−26 (4)
N9^v—Mn2—N7—C2	83.85 (18)	Mn1—N6—C9—N14	−109.8 (19)
N11^i—Mn2—N7—C1	−5.01 (19)	C10—N14—C9—N6	−173.9 (18)
N15^ii—Mn2—N7—C1	−85.2 (4)	Mn2^iii—N13—C8—N12	−132.0 (17)
N13^iii—Mn2—N7—C1	88.7 (2)	C7—N12—C8—N13	176.1 (18)
N8^iv—Mn2—N7—C1	178.5 (2)	Mn1—N3—C4—N9^vi	−92 (4)
N9^v—Mn2—N7—C1	−99.43 (19)	Mn1—N5—C7—N12	−63 (3)
N6—Mn1—N5—C7	2.5 (12)	C8—N12—C7—N5	−175 (2)

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

(2) catena-Poly[bis(butyltriphenylphosphonium) [[(dicyanamido-κN¹)manganese(II)]-di-µ₂-dicyanamido-κ⁴N¹:N⁵]]

Crystal data

(C22H24P)2[Mn(C2N3)4]	F(000) = 998
Mr = 957.90	Dx = 1.270 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5687 reflections
a = 15.711 (3) Å	θ = 3.0–27.5°
b = 7.6050 (15) Å	µ = 0.38 mm^−1
c = 21.499 (4) Å	T = 293 K
β = 102.86 (3)°	Block, colourless
V = 2504.3 (9) Å^3	0.30 × 0.28 × 0.25 mm
Z = 2

Data collection

Rigaku SCXmini diffractometer	2956 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.078
Graphite monochromator	θmax = 27.5°, θmin = 3.0°
ω scans	h = −16→20
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
Tmin = 0.896, Tmax = 0.912	l = −24→27
15859 measured reflections	3 standard reflections every 180 reflections
5687 independent reflections	intensity decay: none

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)] = 0.070	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.193	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0885P)^2] where P = (Fo^2 + 2Fc^2)/3
5687 reflections	(Δ/σ)max = 0.018
305 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Mn1	0.5000	1.0000	0.0000	0.0369 (2)
P1	0.98034 (6)	0.31631 (12)	0.18127 (5)	0.0384 (3)
C1	0.9210 (2)	0.1715 (5)	0.12067 (17)	0.0409 (9)
C23	0.6199 (3)	0.6691 (5)	0.0626 (2)	0.0522 (11)
C13	0.9085 (2)	0.4607 (4)	0.21230 (17)	0.0381 (9)
N1	0.5958 (2)	0.8112 (4)	0.06046 (17)	0.0547 (9)
C18	0.8580 (3)	0.5834 (5)	0.17119 (19)	0.0487 (10)
H18	0.8592	0.5838	0.1281	0.058*
N4	0.4247 (2)	1.0155 (5)	0.07382 (18)	0.0620 (10)
C25	0.3791 (3)	1.0114 (5)	0.1080 (2)	0.0469 (10)
C19	1.0446 (3)	0.1836 (5)	0.24372 (19)	0.0494 (10)
H19A	1.0927	0.1330	0.2283	0.059*
H19B	1.0694	0.2594	0.2794	0.059*
C14	0.9073 (3)	0.4616 (5)	0.27653 (19)	0.0462 (10)
H14	0.9407	0.3811	0.3042	0.055*
N3	0.5785 (2)	1.2368 (4)	0.04030 (17)	0.0539 (9)
C15	0.8559 (3)	0.5830 (6)	0.2995 (2)	0.0606 (12)
H15	0.8550	0.5842	0.3426	0.073*
C2	0.8313 (2)	0.1797 (5)	0.09785 (18)	0.0472 (10)
H2	0.7990	0.2657	0.1130	0.057*
N5	0.3353 (3)	0.9923 (6)	0.15235 (19)	0.0762 (12)
C6	0.9684 (3)	0.0395 (5)	0.0976 (2)	0.0555 (11)
H6	1.0285	0.0312	0.1129	0.067*
C24	0.6096 (3)	1.3704 (5)	0.0520 (2)	0.0525 (11)
C20	0.9950 (3)	0.0351 (6)	0.2677 (2)	0.0670 (14)
H20A	0.9683	−0.0394	0.2321	0.080*
H20B	0.9487	0.0847	0.2855	0.080*
C17	0.8068 (3)	0.7029 (6)	0.1939 (2)	0.0575 (11)
H17	0.7732	0.7832	0.1663	0.069*
N2	0.6550 (3)	0.5137 (5)	0.0674 (3)	0.110 (2)
C7	1.0580 (3)	0.4417 (6)	0.0837 (2)	0.0672 (13)
H7	1.0233	0.3617	0.0566	0.081*
C3	0.7895 (3)	0.0601 (6)	0.0525 (2)	0.0591 (12)
H3	0.7294	0.0656	0.0373	0.071*
C16	0.8055 (3)	0.7032 (6)	0.2580 (2)	0.0601 (12)
H16	0.7709	0.7840	0.2735	0.072*
C26	0.2628 (3)	1.0763 (6)	0.1507 (2)	0.0580 (12)
C5	0.9263 (3)	−0.0765 (6)	0.0528 (2)	0.0663 (13)
H5	0.9581	−0.1632	0.0375	0.080*
C4	0.8376 (3)	−0.0671 (6)	0.0299 (2)	0.0633 (13)
H4	0.8098	−0.1466	−0.0009	0.076*
C11	1.1020 (4)	0.5746 (7)	0.1848 (2)	0.0814 (16)
H11	1.0975	0.5879	0.2269	0.098*
C21	1.0552 (4)	−0.0768 (6)	0.3188 (3)	0.0907 (18)
H21A	1.0223	−0.1780	0.3278	0.109*
H21B	1.1027	−0.1204	0.3010	0.109*
C8	1.1166 (4)	0.5498 (8)	0.0605 (3)	0.0869 (17)
H8	1.1215	0.5401	0.0183	0.104*
C10	1.1609 (4)	0.6794 (8)	0.1609 (3)	0.104 (2)
H10	1.1971	0.7580	0.1876	0.125*
C9	1.1649 (4)	0.6655 (7)	0.0990 (3)	0.0866 (17)
H9	1.2023	0.7388	0.0831	0.104*
C22	1.0917 (4)	0.0086 (8)	0.3774 (3)	0.107 (2)
H22A	1.1321	0.0971	0.3705	0.160*
H22B	1.1216	−0.0761	0.4076	0.160*
H22C	1.0459	0.0625	0.3938	0.160*
N6	0.1989 (3)	1.1341 (6)	0.1550 (3)	0.1090 (18)
C12	1.0516 (3)	0.4543 (5)	0.1471 (2)	0.0467 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0394 (5)	0.0244 (4)	0.0471 (5)	0.0001 (3)	0.0101 (4)	−0.0043 (4)
P1	0.0339 (5)	0.0373 (5)	0.0436 (6)	−0.0010 (4)	0.0081 (4)	−0.0026 (4)
C1	0.038 (2)	0.042 (2)	0.043 (2)	−0.0033 (17)	0.0096 (17)	−0.0004 (17)
C23	0.040 (2)	0.033 (2)	0.073 (3)	−0.0076 (18)	−0.010 (2)	−0.007 (2)
C13	0.038 (2)	0.036 (2)	0.039 (2)	−0.0030 (16)	0.0064 (16)	−0.0019 (16)
N1	0.051 (2)	0.0312 (18)	0.076 (3)	0.0011 (16)	0.0026 (18)	−0.0024 (17)
C18	0.055 (3)	0.052 (2)	0.039 (2)	0.008 (2)	0.0108 (19)	−0.0033 (19)
N4	0.067 (3)	0.058 (2)	0.069 (3)	−0.001 (2)	0.033 (2)	−0.005 (2)
C25	0.049 (2)	0.040 (2)	0.049 (2)	−0.001 (2)	0.005 (2)	−0.004 (2)
C19	0.052 (2)	0.046 (2)	0.046 (2)	0.0041 (19)	0.0004 (19)	−0.0011 (19)
C14	0.046 (2)	0.051 (2)	0.042 (2)	−0.0005 (19)	0.0103 (18)	−0.0005 (18)
N3	0.062 (2)	0.0261 (17)	0.069 (2)	−0.0046 (16)	0.0046 (18)	−0.0071 (16)
C15	0.069 (3)	0.074 (3)	0.040 (3)	−0.001 (3)	0.014 (2)	−0.014 (2)
C2	0.039 (2)	0.054 (2)	0.049 (2)	−0.0014 (19)	0.0105 (18)	−0.007 (2)
N5	0.070 (3)	0.096 (3)	0.072 (3)	0.024 (2)	0.036 (2)	0.025 (2)
C6	0.044 (2)	0.060 (3)	0.064 (3)	0.002 (2)	0.014 (2)	−0.015 (2)
C24	0.047 (2)	0.031 (2)	0.068 (3)	0.0077 (19)	−0.010 (2)	−0.001 (2)
C20	0.075 (3)	0.053 (3)	0.066 (3)	−0.016 (2)	−0.001 (2)	0.011 (2)
C17	0.059 (3)	0.053 (3)	0.056 (3)	0.013 (2)	0.005 (2)	0.000 (2)
N2	0.059 (3)	0.036 (2)	0.200 (6)	0.0019 (19)	−0.044 (3)	−0.022 (3)
C7	0.069 (3)	0.071 (3)	0.064 (3)	−0.013 (3)	0.021 (2)	−0.006 (2)
C3	0.046 (3)	0.065 (3)	0.062 (3)	−0.011 (2)	0.003 (2)	−0.012 (2)
C16	0.057 (3)	0.057 (3)	0.069 (3)	0.009 (2)	0.019 (2)	−0.020 (2)
C26	0.054 (3)	0.058 (3)	0.066 (3)	0.007 (2)	0.022 (2)	0.008 (2)
C5	0.070 (3)	0.058 (3)	0.072 (3)	0.002 (2)	0.019 (3)	−0.019 (2)
C4	0.080 (4)	0.056 (3)	0.052 (3)	−0.011 (3)	0.010 (2)	−0.015 (2)
C11	0.104 (4)	0.084 (4)	0.061 (3)	−0.041 (3)	0.030 (3)	−0.003 (3)
C21	0.138 (5)	0.045 (3)	0.080 (4)	−0.004 (3)	0.004 (4)	0.013 (3)
C8	0.095 (4)	0.100 (4)	0.074 (4)	−0.020 (4)	0.036 (3)	0.008 (3)
C10	0.113 (5)	0.107 (5)	0.086 (4)	−0.061 (4)	0.008 (4)	0.008 (4)
C9	0.083 (4)	0.098 (4)	0.079 (4)	−0.029 (3)	0.019 (3)	0.018 (3)
C22	0.142 (6)	0.087 (4)	0.080 (4)	−0.004 (4)	0.001 (4)	0.016 (4)
N6	0.091 (4)	0.105 (4)	0.152 (5)	0.038 (3)	0.071 (3)	0.026 (3)
C12	0.046 (2)	0.044 (2)	0.052 (3)	−0.0024 (18)	0.0139 (19)	−0.0043 (19)

Geometric parameters (Å, º)

Mn1—N4^i	2.183 (4)	C6—H6	0.9300
Mn1—N4	2.183 (4)	C24—N2^ii	1.304 (5)
Mn1—N3	2.245 (3)	C20—C21	1.536 (6)
Mn1—N3^i	2.245 (3)	C20—H20A	0.9700
Mn1—N1	2.268 (3)	C20—H20B	0.9700
Mn1—N1^i	2.268 (3)	C17—C16	1.382 (6)
P1—C19	1.799 (4)	C17—H17	0.9300
P1—C1	1.800 (4)	N2—C24^iii	1.304 (5)
P1—C13	1.806 (4)	C7—C12	1.392 (6)
P1—C12	1.806 (4)	C7—C8	1.405 (7)
C1—C2	1.386 (5)	C7—H7	0.9300
C1—C6	1.405 (5)	C3—C4	1.380 (6)
C23—N1	1.143 (4)	C3—H3	0.9300
C23—N2	1.299 (5)	C16—H16	0.9300
C13—C14	1.385 (5)	C26—N6	1.118 (6)
C13—C18	1.404 (5)	C5—C4	1.372 (6)
C18—C17	1.373 (5)	C5—H5	0.9300
C18—H18	0.9300	C4—H4	0.9300
N4—C25	1.136 (5)	C11—C12	1.355 (6)
C25—N5	1.302 (6)	C11—C10	1.402 (7)
C19—C20	1.526 (5)	C11—H11	0.9300
C19—H19A	0.9700	C21—C22	1.421 (7)
C19—H19B	0.9700	C21—H21A	0.9700
C14—C15	1.388 (6)	C21—H21B	0.9700
C14—H14	0.9300	C8—C9	1.325 (7)
N3—C24	1.131 (4)	C8—H8	0.9300
C15—C16	1.394 (6)	C10—C9	1.350 (7)
C15—H15	0.9300	C10—H10	0.9300
C2—C3	1.388 (5)	C9—H9	0.9300
C2—H2	0.9300	C22—H22A	0.9600
N5—C26	1.299 (6)	C22—H22B	0.9600
C6—C5	1.365 (6)	C22—H22C	0.9600
N4—Mn1—N4^i	180.0	N3—C24—N2^ii	172.7 (4)
N4^i—Mn1—N3	89.07 (13)	C19—C20—C21	111.9 (4)
N4—Mn1—N3	90.93 (13)	C19—C20—H20A	109.2
N4^i—Mn1—N3^i	90.93 (13)	C21—C20—H20A	109.2
N4—Mn1—N3^i	89.07 (13)	C19—C20—H20B	109.2
N3—Mn1—N3^i	180.0	C21—C20—H20B	109.2
N4^i—Mn1—N1	89.13 (14)	H20A—C20—H20B	107.9
N4—Mn1—N1	90.87 (14)	C18—C17—C16	119.7 (4)
N3—Mn1—N1	92.83 (12)	C18—C17—H17	120.1
N3^i—Mn1—N1	87.17 (12)	C16—C17—H17	120.1
N4^i—Mn1—N1^i	90.87 (14)	C23—N2—C24^iii	122.8 (4)
N4—Mn1—N1^i	89.13 (14)	C12—C7—C8	120.1 (5)
N3—Mn1—N1^i	87.17 (12)	C12—C7—H7	119.9
N3^i—Mn1—N1^i	92.83 (12)	C8—C7—H7	119.9
N1—Mn1—N1^i	180.0	C4—C3—C2	119.8 (4)
C19—P1—C1	108.15 (18)	C4—C3—H3	120.1
C19—P1—C13	111.02 (18)	C2—C3—H3	120.1
C1—P1—C13	111.93 (17)	C17—C16—C15	120.3 (4)
C19—P1—C12	109.49 (19)	C17—C16—H16	119.9
C1—P1—C12	109.21 (18)	C15—C16—H16	119.9
C13—P1—C12	107.02 (18)	N6—C26—N5	171.3 (5)
C2—C1—C6	119.0 (4)	C6—C5—C4	120.9 (4)
C2—C1—P1	123.4 (3)	C6—C5—H5	119.5
C6—C1—P1	117.5 (3)	C4—C5—H5	119.5
N1—C23—N2	174.3 (4)	C5—C4—C3	120.1 (4)
C14—C13—C18	119.5 (3)	C5—C4—H4	119.9
C14—C13—P1	121.3 (3)	C3—C4—H4	119.9
C18—C13—P1	119.0 (3)	C12—C11—C10	120.7 (5)
C23—N1—Mn1	142.5 (3)	C12—C11—H11	119.7
C17—C18—C13	120.6 (4)	C10—C11—H11	119.7
C17—C18—H18	119.7	C22—C21—C20	116.3 (5)
C13—C18—H18	119.7	C22—C21—H21A	108.2
C25—N4—Mn1	172.4 (4)	C20—C21—H21A	108.2
N4—C25—N5	171.8 (5)	C22—C21—H21B	108.2
C20—C19—P1	115.0 (3)	C20—C21—H21B	108.2
C20—C19—H19A	108.5	H21A—C21—H21B	107.4
P1—C19—H19A	108.5	C9—C8—C7	119.8 (5)
C20—C19—H19B	108.5	C9—C8—H8	120.1
P1—C19—H19B	108.5	C7—C8—H8	120.1
H19A—C19—H19B	107.5	C9—C10—C11	119.7 (5)
C15—C14—C13	119.7 (4)	C9—C10—H10	120.2
C15—C14—H14	120.1	C11—C10—H10	120.2
C13—C14—H14	120.1	C8—C9—C10	121.5 (5)
C24—N3—Mn1	168.4 (3)	C8—C9—H9	119.3
C14—C15—C16	120.1 (4)	C10—C9—H9	119.3
C14—C15—H15	120.0	C21—C22—H22A	109.5
C16—C15—H15	120.0	C21—C22—H22B	109.5
C1—C2—C3	120.2 (4)	H22A—C22—H22B	109.5
C1—C2—H2	119.9	C21—C22—H22C	109.5
C3—C2—H2	119.9	H22A—C22—H22C	109.5
C26—N5—C25	121.9 (4)	H22B—C22—H22C	109.5
C5—C6—C1	119.9 (4)	C11—C12—C7	118.2 (4)
C5—C6—H6	120.0	C11—C12—P1	118.8 (3)
C1—C6—H6	120.0	C7—C12—P1	123.0 (3)
C19—P1—C1—C2	126.8 (3)	N1—Mn1—N3—C24	164.2 (18)
C13—P1—C1—C2	4.2 (4)	N1^i—Mn1—N3—C24	−15.8 (18)
C12—P1—C1—C2	−114.1 (3)	C13—C14—C15—C16	0.2 (6)
C19—P1—C1—C6	−50.6 (4)	C6—C1—C2—C3	−0.6 (6)
C13—P1—C1—C6	−173.2 (3)	P1—C1—C2—C3	−178.0 (3)
C12—P1—C1—C6	68.5 (4)	N4—C25—N5—C26	175 (3)
C19—P1—C13—C14	0.3 (4)	C2—C1—C6—C5	0.9 (6)
C1—P1—C13—C14	121.2 (3)	P1—C1—C6—C5	178.4 (4)
C12—P1—C13—C14	−119.2 (3)	Mn1—N3—C24—N2^ii	−139 (3)
C19—P1—C13—C18	175.3 (3)	P1—C19—C20—C21	177.5 (4)
C1—P1—C13—C18	−63.7 (3)	C13—C18—C17—C16	0.5 (6)
C12—P1—C13—C18	55.9 (3)	N1—C23—N2—C24^iii	178 (100)
N2—C23—N1—Mn1	142 (6)	C1—C2—C3—C4	−0.2 (6)
N4^i—Mn1—N1—C23	−67.0 (6)	C18—C17—C16—C15	0.0 (7)
N4—Mn1—N1—C23	113.0 (6)	C14—C15—C16—C17	−0.3 (7)
N3—Mn1—N1—C23	−156.0 (6)	C25—N5—C26—N6	165 (4)
N3^i—Mn1—N1—C23	24.0 (6)	C1—C6—C5—C4	−0.4 (7)
N1^i—Mn1—N1—C23	78 (20)	C6—C5—C4—C3	−0.4 (8)
C14—C13—C18—C17	−0.7 (6)	C2—C3—C4—C5	0.7 (7)
P1—C13—C18—C17	−175.8 (3)	C19—C20—C21—C22	66.0 (7)
N4^i—Mn1—N4—C25	35 (100)	C12—C7—C8—C9	−1.0 (8)
N3—Mn1—N4—C25	164 (3)	C12—C11—C10—C9	2.8 (10)
N3^i—Mn1—N4—C25	−16 (3)	C7—C8—C9—C10	1.8 (10)
N1—Mn1—N4—C25	−103 (3)	C11—C10—C9—C8	−2.7 (10)
N1^i—Mn1—N4—C25	77 (3)	C10—C11—C12—C7	−2.1 (8)
Mn1—N4—C25—N5	106 (4)	C10—C11—C12—P1	177.3 (5)
C1—P1—C19—C20	−49.3 (4)	C8—C7—C12—C11	1.2 (7)
C13—P1—C19—C20	73.9 (4)	C8—C7—C12—P1	−178.2 (4)
C12—P1—C19—C20	−168.2 (3)	C19—P1—C12—C11	−62.3 (4)
C18—C13—C14—C15	0.3 (6)	C1—P1—C12—C11	179.5 (4)
P1—C13—C14—C15	175.3 (3)	C13—P1—C12—C11	58.1 (4)
N4^i—Mn1—N3—C24	75.1 (18)	C19—P1—C12—C7	117.1 (4)
N4—Mn1—N3—C24	−104.9 (18)	C1—P1—C12—C7	−1.1 (4)
N3^i—Mn1—N3—C24	−66.7 (18)	C13—P1—C12—C7	−122.5 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19A···N6^iv	0.97	2.54	3.424 (7)	152
C19—H19B···N5^v	0.97	2.56	3.491 (6)	161

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