Bis{1-methyl-5-[3-(1-methyl-1H-tetra­zolo[5,1-a]iso­indol-5-yl)allyl­idene]-5H-tetra­zolo[5,1-a]isoindol-1-ium} tetra­cyano­nickelate(II)

Voitenko, Z.V.; Yegorova, T.V.; Zatovsky, I.V.; Jaud, J.; Wolf, J.G.

doi:10.1107/S1600536805039656

Bis{1-methyl-5-[3-(1-methyl-1H-tetrazolo[5,1-a]isoindol-5-yl)allylidene]-5H-tetrazolo[5,1-a]isoindol-1-ium} tetracyanonickelate(II)

Z. V. Voitenko, T. V. Yegorova, I. V. Zatovsky, J. Jaud and J. G. Wolf

The molecular structure of the title compound, (C₂₁H₁₇N₈)₂[Ni(CN)₄], consists of two organic cations, C₂₁H₁₇N₈⁺ or [MTIT]⁺, and a centrosymmetric inorganic dianion, [Ni(CN)₄]²⁻. In the crystal structure, the ions stack along the b axis and are connected by a number of C—H

N hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805039656/su6242sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805039656/su6242Isup2.hkl Contains datablock I

CCDC reference: 296672

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.008 Å
R factor = 0.097
wR factor = 0.176
Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT432_ALERT_2_B Short Inter X...Y Contact  N002   ..  C19     ..       2.92 Ang.

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct...          8
PLAT166_ALERT_4_C S.U's Given on Coordinates for calc-flagged ....         H3
PLAT166_ALERT_4_C S.U's Given on Coordinates for calc-flagged ....         H4
PLAT166_ALERT_4_C S.U's Given on Coordinates for calc-flagged ....         H5
PLAT166_ALERT_4_C S.U's Given on Coordinates for calc-flagged ....         H6
PLAT166_ALERT_4_C S.U's Given on Coordinates for calc-flagged ....        H14
PLAT166_ALERT_4_C S.U's Given on Coordinates for calc-flagged ....        H15
PLAT166_ALERT_4_C S.U's Given on Coordinates for calc-flagged ....        H16
PLAT166_ALERT_4_C S.U's Given on Coordinates for calc-flagged ....        H17
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          8
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........         12

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
  12 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
  10 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

The study of the title compound, (I), was undertaken to establish its three dimensional structure. To our knowledge only one other cyanine molecular complex, [cy⁺·AuCl₂⁻] has been reported to date (Falkenberg et al., 1973).

The molecular strucure of (I), consisting of two 1-methyl-5-[3-(1-methyl-1H-tetrazolo[5,1-a]isoindol-5-yl)- allylidene]-5H-tetrazolo[5,1-a]isoindol-1-ium monocations, [MTIT]⁺, and an [Ni(CN)₄]²⁻ dianion, is illustrated in Fig. 1. Selected bond lengths and angles are given in Table 1. The organic [MTIT]⁺ cation is planar and the C—C bonds lengths range from 1.370 (9) to 1.457 (7) Å, thus indicating the aromaticity of the dye molecule. Both [MTIT]⁺ cations possess identical geometry in the carbon–nitrogen skeleton.

The geometry of the [Ni(CN)₄]²⁻ anion is typical for a square-planar Ni atom with four CN groups (Table 1). The Ni atom lies on a twofold rotation axis. These flat anions are located parallel to one another at a distance of 6.83 (s.u.?) Å, forming stacks. The stacks are inclined to the ac plane at 60 (s.u.?) and 120 (s.u.?)°, and are staggered (Fig. 2).

The [MTIT]⁺ dye cations are stacked stepwise with two oppositely oriented molecules. The [Ni(CN)₄]²⁻ anion is located between these steps, and the Ni···C distances are ca 3.796 and 3.739 Å, thus indicating additional interactions of the Ni atoms with the conjugated system of the dye (Fig. 3).

The N atoms of the CN groups are bound to the [MTIT]⁺ dye cations via C—H···N hydrogen bonds (the N···H distances are 2.432–2.530 Å [not in accord with Table 2]). Each [Ni(CN)₄]²⁻ anion has three N···H contacts with two dye molecules that lie in one plane (Table 2). These molecules are axial to the Ni atoms. One more pair of N···H contacts is formed with two dye molecules that are almost perpendicular to the plane of the [Ni(CN)₄]²⁻ complex anion. This situtation is shown in Fig. 4 and details are given in Table 2.

In view of these stabilizating interactions, (I) can be considered not as a simple cation–anion salt but as a molecular complex with specific intermolecular interactions.

Experimental top

The starting material, MTIT perchlorate, was prepared according to a known protocol (Babichev & Romanov, 1975). The title compound, (I), was prepared from equimolar quantities of [MTIT]⁺·ClO₄⁻ and K₂[Ni(CN)₄] in an acetonitrile/propanol/water system (Yegorova et al., 2002). [MTIT]⁺·ClO₄⁻ (306 mg, 0.64 mmol) in acetonitrile (150 ml) was mixed with K₂[Ni(CN)₄] (120 mg) in a 2-propanol–water mixture (1:1, 30 ml). This mixture was heated to boiling point for 10 min and then cooled slowly to 273 K. Formation of a black–green crystalline precipitate was observed. This crystalline product was decantated, washed with water and 2-propanol, and dried at 313 K. The amount of Ni in (I) was determined by ICP atomic emission spectroscopy, and no K was found in the analyzed samples. By IR spectroscopy, the cyanine fingerprint was observed with the addition of a CN band at 2110 cm⁻¹. The characteristic perchlorate bands at 630 and 1100 cm⁻¹ were absent. The UV–vis spectra show the dye bands at 590 (shoulder) and 636 nm, and a new band, at 770 nm, was attributed to an Ni^II transition.

Computing details top

Data collection: Please provide; cell refinement: Please provide; data reduction: Please provide; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. A view of the molecular structure of (I), showing the labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. A view along b of the crystal packing of compound (I).
	Fig. 3. A view of the interaction of the Ni atom with the π-system of the dye cation (dashed lines).
	Fig. 4. A view of the C—H···N interactions (dashed lines) in the crystal structure of compound (I).

Bis(1-methyl-5-[3-(1-methyl-1H-tetrazolo[5,1-a]isoindol-5-yl)allylidene]-5H- tetrazolo[5,1-a]isoindol-1-ium) tetracyanonickel(II) top

Crystal data top

(C₂₁H₁₇N₈)₂[Ni(CN)₄]	F(000) = 956
M_r = 925.61	D_x = 1.488 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4688 reflections
a = 16.296 (2) Å	θ = 0–29.2°
b = 7.5708 (7) Å	µ = 0.53 mm⁻¹
c = 18.537 (3) Å	T = 298 K
β = 115.42 (2)°	Prism, black-green
V = 2065.6 (6) Å³	0.2 × 0.2 × 0.1 mm
Z = 2

Data collection top

Nonius KappaCCD diffractometer	3172 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.069
ϕ or ω?, thick slices scans	θ_max = 27.5°, θ_min = 6.1°
Absorption correction: multi-scan SORTAV (Blessing, 1995)	h = −21→21
T_min = 0.901, T_max = 0.949	k = −9→9
18746 measured reflections	l = −24→21
4672 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.097	w = 1/[σ²(F_o²) + (0.0001P)² + 6.0123P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.176	(Δ/σ)_max < 0.001
S = 1.33	Δρ_max = 0.45 e Å⁻³
4672 reflections	Δρ_min = −0.73 e Å⁻³
314 parameters

Crystal data top

(C₂₁H₁₇N₈)₂[Ni(CN)₄]	V = 2065.6 (6) Å³
M_r = 925.61	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 16.296 (2) Å	µ = 0.53 mm⁻¹
b = 7.5708 (7) Å	T = 298 K
c = 18.537 (3) Å	0.2 × 0.2 × 0.1 mm
β = 115.42 (2)°

Data collection top

Nonius KappaCCD diffractometer	4672 independent reflections
Absorption correction: multi-scan SORTAV (Blessing, 1995)	3172 reflections with I > 2σ(I)
T_min = 0.901, T_max = 0.949	R_int = 0.069
18746 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.097	0 restraints
wR(F²) = 0.176	H-atom parameters constrained
S = 1.33	Δρ_max = 0.45 e Å⁻³
4672 reflections	Δρ_min = −0.73 e Å⁻³
314 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	1.0824 (3)	0.0890 (6)	0.4102 (2)	0.0358 (14)
N2	1.1162 (3)	0.0955 (6)	0.4918 (2)	0.0412 (16)
N3	1.0580 (3)	0.1757 (6)	0.5109 (2)	0.0406 (16)
N4	0.9862 (3)	0.2196 (5)	0.4409 (2)	0.0336 (12)
N5	0.9922 (3)	0.4016 (6)	0.7336 (2)	0.0342 (12)
N6	1.0603 (3)	0.3012 (6)	0.7299 (3)	0.0465 (17)
N7	1.1195 (3)	0.2787 (6)	0.8027 (3)	0.0476 (17)
N8	1.0914 (3)	0.3619 (6)	0.8527 (2)	0.0379 (14)
C1	1.0003 (3)	0.1665 (7)	0.3775 (3)	0.0332 (17)
C2	0.9240 (3)	0.2161 (6)	0.3054 (3)	0.0311 (17)
C3	0.9035 (3)	0.1923 (7)	0.2239 (3)	0.0338 (17)
C003	1.1444 (4)	0.3566 (9)	0.9394 (3)	0.0525 (19)
C4	0.8219 (3)	0.2625 (7)	0.1686 (3)	0.0372 (17)
C004	1.1370 (3)	0.0158 (7)	0.3721 (3)	0.0408 (17)
C5	0.7639 (4)	0.3553 (7)	0.1938 (3)	0.0384 (17)
C6	0.7847 (4)	0.3788 (7)	0.2735 (3)	0.0383 (17)
C7	0.8655 (3)	0.3088 (6)	0.3305 (3)	0.0322 (17)
C8	0.9039 (3)	0.3122 (7)	0.4174 (3)	0.0341 (17)
C9	0.8729 (4)	0.3863 (7)	0.4694 (3)	0.0380 (17)
C10	0.9139 (4)	0.3844 (7)	0.5522 (3)	0.0375 (17)
C11	0.8734 (3)	0.4627 (7)	0.5970 (3)	0.0360 (17)
C12	0.9074 (3)	0.4702 (7)	0.6790 (3)	0.0334 (17)
C13	0.8719 (3)	0.5500 (7)	0.7309 (3)	0.0349 (17)
C14	0.7885 (4)	0.6303 (7)	0.7130 (3)	0.0377 (17)
C15	0.7699 (4)	0.6896 (7)	0.7742 (3)	0.0404 (17)
C16	0.8344 (4)	0.6727 (8)	0.8543 (3)	0.046 (2)
C17	0.9170 (4)	0.5938 (7)	0.8744 (3)	0.0408 (17)
C18	0.9357 (3)	0.5319 (7)	0.8120 (3)	0.0348 (16)
C19	1.0098 (3)	0.4363 (7)	0.8104 (3)	0.0342 (17)
Ni1	0.00000	0.00000	0.00000	0.0340 (3)
N001	−0.1639 (3)	0.2038 (7)	−0.0087 (3)	0.0562 (18)
N002	−0.0465 (3)	0.0775 (6)	−0.1739 (3)	0.0426 (16)
C001	−0.1010 (4)	0.1264 (7)	−0.0055 (3)	0.0380 (16)
C002	−0.0309 (3)	0.0487 (7)	−0.1085 (3)	0.0382 (17)
H00D	1.11960	0.26870	0.96170	0.0790*
H00E	1.14210	0.47000	0.96160	0.0790*
H3	0.945 (2)	0.129 (3)	0.2070 (9)	0.0410*
H00F	1.20640	0.32750	0.95170	0.0790*
H4	0.8046 (10)	0.2473 (11)	0.112 (3)	0.0450*
H00A	1.10350	0.02280	0.31520	0.0610*
H5	0.713 (3)	0.400 (3)	0.157 (2)	0.0460*
H00B	1.15100	−0.10550	0.38770	0.0610*
H6	0.744 (2)	0.442 (4)	0.2894 (9)	0.0460*
H00C	1.19240	0.08200	0.38860	0.0610*
H9	0.81740	0.44470	0.44570	0.0460*
H10	0.97000	0.32940	0.57860	0.0450*
H11	0.81720	0.51570	0.56830	0.0430*
H14	0.747 (2)	0.6432 (10)	0.662 (3)	0.0450*
H15	0.713 (3)	0.742 (3)	0.7627 (8)	0.0490*
H16	0.8206 (10)	0.716 (3)	0.894 (3)	0.0560*
H17	0.961 (3)	0.5815 (10)	0.929 (3)	0.0490*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.041 (3)	0.036 (2)	0.036 (2)	0.002 (2)	0.022 (2)	0.003 (2)
N2	0.046 (3)	0.041 (3)	0.035 (2)	0.001 (2)	0.016 (2)	0.006 (2)
N3	0.041 (3)	0.048 (3)	0.032 (2)	0.003 (2)	0.015 (2)	0.003 (2)
N4	0.040 (2)	0.037 (2)	0.027 (2)	−0.002 (2)	0.0174 (19)	0.0024 (19)
N5	0.037 (2)	0.036 (2)	0.038 (2)	0.002 (2)	0.024 (2)	0.004 (2)
N6	0.047 (3)	0.054 (3)	0.045 (3)	0.003 (2)	0.026 (2)	0.003 (2)
N7	0.049 (3)	0.054 (3)	0.050 (3)	0.000 (2)	0.031 (3)	−0.005 (2)
N8	0.035 (2)	0.041 (3)	0.039 (2)	−0.002 (2)	0.017 (2)	0.000 (2)
C1	0.038 (3)	0.036 (3)	0.032 (3)	−0.006 (2)	0.021 (2)	0.000 (2)
C2	0.038 (3)	0.029 (3)	0.030 (3)	−0.001 (2)	0.018 (2)	0.000 (2)
C3	0.038 (3)	0.040 (3)	0.031 (3)	−0.003 (2)	0.022 (2)	0.001 (2)
C003	0.049 (3)	0.064 (4)	0.035 (3)	0.001 (3)	0.009 (3)	0.000 (3)
C4	0.044 (3)	0.041 (3)	0.030 (3)	−0.008 (3)	0.019 (2)	−0.006 (2)
C004	0.040 (3)	0.044 (3)	0.042 (3)	0.000 (3)	0.021 (2)	0.002 (3)
C5	0.044 (3)	0.037 (3)	0.031 (3)	0.000 (3)	0.013 (2)	0.002 (2)
C6	0.040 (3)	0.045 (3)	0.036 (3)	0.000 (3)	0.022 (2)	0.002 (2)
C7	0.040 (3)	0.030 (3)	0.035 (3)	−0.003 (2)	0.024 (2)	−0.001 (2)
C8	0.040 (3)	0.037 (3)	0.027 (3)	0.002 (2)	0.016 (2)	0.000 (2)
C9	0.045 (3)	0.035 (3)	0.041 (3)	0.004 (2)	0.025 (3)	0.007 (2)
C10	0.046 (3)	0.038 (3)	0.037 (3)	−0.007 (3)	0.026 (2)	−0.003 (2)
C11	0.040 (3)	0.038 (3)	0.035 (3)	0.000 (2)	0.021 (2)	0.004 (2)
C12	0.037 (3)	0.035 (3)	0.035 (3)	−0.002 (2)	0.022 (2)	0.005 (2)
C13	0.037 (3)	0.037 (3)	0.031 (3)	−0.006 (2)	0.015 (2)	0.003 (2)
C14	0.044 (3)	0.040 (3)	0.031 (3)	−0.002 (3)	0.018 (2)	−0.002 (2)
C15	0.040 (3)	0.040 (3)	0.045 (3)	0.003 (3)	0.022 (3)	−0.003 (3)
C16	0.066 (4)	0.049 (4)	0.041 (3)	−0.006 (3)	0.039 (3)	−0.008 (3)
C17	0.041 (3)	0.050 (3)	0.031 (3)	−0.008 (3)	0.015 (2)	−0.010 (3)
C18	0.042 (3)	0.037 (3)	0.031 (2)	−0.008 (2)	0.021 (2)	−0.002 (2)
C19	0.034 (3)	0.035 (3)	0.034 (3)	−0.005 (2)	0.015 (2)	0.001 (2)
Ni1	0.0349 (5)	0.0439 (6)	0.0264 (5)	−0.0017 (5)	0.0161 (4)	−0.0018 (4)
N001	0.051 (3)	0.085 (4)	0.031 (2)	0.022 (3)	0.016 (2)	−0.008 (3)
N002	0.044 (3)	0.055 (3)	0.035 (2)	−0.004 (2)	0.023 (2)	−0.003 (2)
C001	0.044 (3)	0.047 (3)	0.020 (2)	−0.004 (3)	0.011 (2)	−0.004 (2)
C002	0.036 (3)	0.046 (3)	0.038 (3)	−0.002 (2)	0.021 (2)	−0.007 (2)

Geometric parameters (Å, º) top

Ni1—C001ⁱ	1.868 (7)	C9—C10	1.386 (7)
Ni1—C002ⁱ	1.888 (5)	C10—C11	1.395 (8)
Ni1—C001	1.868 (7)	C11—C12	1.378 (7)
Ni1—C002	1.888 (5)	C12—C13	1.450 (7)
N1—N2	1.371 (5)	C13—C18	1.421 (7)
N1—C004	1.462 (7)	C13—C14	1.393 (9)
N1—C1	1.344 (7)	C14—C15	1.370 (8)
N2—N3	1.297 (7)	C15—C16	1.409 (7)
N3—N4	1.364 (5)	C16—C17	1.370 (9)
N4—C1	1.352 (7)	C17—C18	1.398 (8)
N4—C8	1.407 (7)	C18—C19	1.419 (8)
N5—C19	1.352 (6)	C3—H3	0.9800
N5—N6	1.371 (7)	C003—H00D	0.9600
N5—C12	1.415 (7)	C003—H00F	0.9600
N6—N7	1.290 (7)	C003—H00E	0.9600
N7—N8	1.353 (7)	C4—H4	0.9700
N8—C003	1.463 (6)	C004—H00C	0.9600
N8—C19	1.344 (7)	C004—H00A	0.9600
N001—C001	1.160 (9)	C004—H00B	0.9600
N002—C002	1.148 (7)	C5—H5	0.8800
C1—C2	1.431 (7)	C6—H6	0.9600
C2—C3	1.412 (7)	C9—H9	0.9300
C2—C7	1.414 (7)	C10—H10	0.9300
C3—C4	1.390 (7)	C11—H11	0.9300
C4—C5	1.409 (8)	C14—H14	0.9000
C5—C6	1.378 (7)	C15—H15	0.9400
C6—C7	1.392 (8)	C16—H16	0.9200
C7—C8	1.457 (7)	C17—H17	0.9600
C8—C9	1.385 (8)

Ni1···C003ⁱⁱ	4.044 (7)	C10···N3	3.184 (8)
Ni1···C16ⁱⁱⁱ	3.803 (6)	C10···C004^ix	3.583 (8)
Ni1···C17ⁱⁱⁱ	3.742 (5)	C10···N4^x	3.388 (7)
Ni1···C16^iv	3.803 (6)	C10···N6	3.193 (7)
Ni1···C17^iv	3.742 (5)	C11···C1^x	3.392 (8)
Ni1···C003^v	4.044 (7)	C12···C1^x	3.504 (8)
Ni1···H00Dⁱⁱ	3.1000	C12···C2^x	3.548 (7)
Ni1···H16ⁱⁱⁱ	3.4800	C13···C15^xvi	3.551 (8)
Ni1···H00D^v	3.1000	C14···C004^x	3.576 (8)
Ni1···H16^iv	3.4800	C14···C15^xvi	3.505 (8)
Ni1···H17^iv	3.3800	C15···C13^xvii	3.551 (8)
Ni1···H17ⁱⁱⁱ	3.3800	C15···C14^xvii	3.505 (8)
N1···N4	2.127 (7)	C15···N002^xviii	3.409 (8)
N001···C4^vi	3.421 (7)	C16···C002^xix	3.478 (8)
N2···N4	2.132 (7)	C16···Ni1ⁱⁱⁱ	3.803 (6)
N002···N7^v	3.291 (7)	C16···Ni1^xix	3.803 (6)
N002···N8^v	2.996 (7)	C17···Ni1ⁱⁱⁱ	3.742 (5)
N002···C15^vii	3.409 (8)	C17···Ni1^xix	3.742 (5)
N002···C19^v	2.921 (7)	C17···C002^xix	3.529 (8)
N002···N5^v	3.207 (7)	C19···C3^x	3.328 (8)
N002···C004^viii	3.394 (7)	C19···C002^xi	3.488 (7)
N3···N4^ix	3.290 (6)	C19···N002^xi	2.921 (7)
N3···N3^ix	3.187 (7)	C19···C4^x	3.458 (8)
N3···C10	3.184 (8)	C001···H17ⁱⁱⁱ	3.0500
N4···C10^x	3.388 (7)	C001···H14^vii	2.8600
N4···N3^ix	3.290 (6)	C002···H3^viii	3.0500
N4···N1	2.127 (7)	C002···H00D^v	2.7800
N5···C2^x	3.408 (7)	C3···H6^xx	2.9900
N5···C3^x	3.437 (7)	C003···H16^xxi	2.9400
N5···N8	2.125 (5)	C4···H6^xx	2.8900
N5···N002^xi	3.207 (7)	C6···H9	3.0400
N6···N8	2.159 (6)	C9···H00F^xv	3.0500
N6···C10	3.193 (7)	C10···H00B^ix	2.8000
N7···C5^x	3.345 (8)	C11···H00B^ix	2.7700
N7···C6^xii	3.196 (9)	C12···H00B^ix	3.0100
N7···N002^xi	3.291 (7)	C13···H15^xvi	2.7400
N8···N002^xi	2.996 (7)	C14···H00C^x	2.9800
N8···C002^xi	3.368 (7)	C14···H11	3.0400
N8···C4^x	3.274 (7)	C14···H15^xvi	2.9800
N8···N5	2.125 (5)	H00D···Ni1^xi	3.1000
N001···H00C^xiii	2.8100	H00D···Ni1ⁱⁱ	3.1000
N001···H14^vii	2.6100	H00D···H16^xxi	2.4200
N001···H11^vii	2.6700	H00D···C002^xi	2.7800
N001···H4^vi	2.5200	H00E···N001ⁱⁱⁱ	2.5900
N001···H00Eⁱⁱⁱ	2.5900	H3···N002^viii	2.5400
N2···H5^xii	2.7800	H3···C002^viii	3.0500
N002···H15^vii	2.7900	H00F···C9^xii	3.0500
N002···H00A^viii	2.4900	H4···N001^xiv	2.5200
N002···H3^viii	2.5400	H00A···N002^viii	2.4900
N3···H5^xii	2.8600	H5···N3^xv	2.8600
N3···H10	2.5600	H5···N2^xv	2.7800
N4···H10	2.8000	H00B···C12^ix	3.0100
N5···H10	2.7900	H00B···C10^ix	2.8000
N6···H10	2.5600	H00B···C11^ix	2.7700
N7···H6^xii	2.7200	H6···N7^xv	2.7200
C1···C12^x	3.504 (8)	H6···C3^xxii	2.9900
C1···C11^x	3.392 (8)	H6···C4^xxii	2.8900
C001···C002	2.678 (8)	H00C···C14^x	2.9800
C001···C002ⁱ	2.635 (8)	H00C···N001^xxiii	2.8100
C2···C12^x	3.548 (7)	H9···H11	2.3400
C2···N5^x	3.408 (7)	H9···C6	3.0400
C002···C19^v	3.488 (7)	H10···N3	2.5600
C002···C003^v	3.494 (9)	H10···N6	2.5600
C002···C001ⁱ	2.635 (8)	H10···N4	2.8000
C002···C17^iv	3.529 (8)	H10···N5	2.7900
C002···C001	2.678 (8)	H11···H9	2.3400
C002···N8^v	3.368 (7)	H11···N001^xviii	2.6700
C002···C16^iv	3.478 (8)	H11···C14	3.0400
C3···N5^x	3.437 (7)	H14···N001^xviii	2.6100
C3···C19^x	3.328 (8)	H14···C001^xviii	2.8600
C003···Ni1^xi	4.044 (7)	H15···N002^xviii	2.7900
C003···C002^xi	3.494 (9)	H15···C13^xvii	2.7400
C003···Ni1ⁱⁱ	4.044 (7)	H15···C14^xvii	2.9800
C4···C19^x	3.458 (8)	H16···C003^xxi	2.9400
C4···N8^x	3.274 (7)	H16···H00D^xxi	2.4200
C4···N001^xiv	3.421 (7)	H16···Ni1ⁱⁱⁱ	3.4800
C004···C10^ix	3.583 (8)	H16···Ni1^xix	3.4800
C004···C14^x	3.576 (8)	H17···C001ⁱⁱⁱ	3.0500
C004···N002^viii	3.394 (7)	H17···Ni1^xix	3.3800
C5···N7^x	3.345 (8)	H17···Ni1ⁱⁱⁱ	3.3800
C6···N7^xv	3.196 (9)

C001—Ni1—C002	90.9 (2)	C13—C14—C15	119.1 (5)
C001—Ni1—C001ⁱ	180	C14—C15—C16	120.9 (6)
C001—Ni1—C002ⁱ	89.1 (2)	C15—C16—C17	121.8 (5)
C001ⁱ—Ni1—C002	89.1 (2)	C16—C17—C18	117.3 (5)
C002—Ni1—C002ⁱ	180	C13—C18—C19	105.7 (4)
C001ⁱ—Ni1—C002ⁱ	90.9 (2)	C13—C18—C17	121.5 (5)
C1—N1—C004	130.0 (4)	C17—C18—C19	132.7 (5)
N2—N1—C1	109.4 (4)	N5—C19—C18	108.9 (5)
N2—N1—C004	120.5 (4)	N5—C19—N8	104.0 (4)
N1—N2—N3	108.9 (4)	N8—C19—C18	147.1 (5)
N2—N3—N4	106.5 (3)	C4—C3—H3	122.00
N3—N4—C8	137.0 (4)	C2—C3—H3	122.00
N3—N4—C1	111.0 (4)	N8—C003—H00D	109.00
C1—N4—C8	112.0 (4)	H00E—C003—H00F	110.00
N6—N5—C12	136.9 (4)	N8—C003—H00F	109.00
N6—N5—C19	110.5 (4)	H00D—C003—H00E	110.00
C12—N5—C19	112.5 (5)	N8—C003—H00E	109.00
N5—N6—N7	106.2 (4)	H00D—C003—H00F	109.00
N6—N7—N8	109.5 (5)	C3—C4—H4	120.00
N7—N8—C19	109.7 (4)	C5—C4—H4	120.00
N7—N8—C003	121.8 (5)	N1—C004—H00B	109.00
C003—N8—C19	128.5 (5)	N1—C004—H00A	109.00
N1—C1—C2	146.5 (5)	H00A—C004—H00C	110.00
N1—C1—N4	104.2 (4)	N1—C004—H00C	109.00
N4—C1—C2	109.3 (5)	H00A—C004—H00B	109.00
C3—C2—C7	122.2 (5)	H00B—C004—H00C	109.00
C1—C2—C3	132.7 (5)	C6—C5—H5	120.00
C1—C2—C7	105.2 (4)	C4—C5—H5	118.00
C2—C3—C4	116.9 (5)	C5—C6—H6	121.00
C3—C4—C5	120.8 (5)	C7—C6—H6	121.00
C4—C5—C6	121.9 (5)	C8—C9—H9	116.00
C5—C6—C7	118.8 (6)	C10—C9—H9	116.00
C2—C7—C8	110.0 (4)	C11—C10—H10	119.00
C2—C7—C6	119.4 (5)	C9—C10—H10	119.00
C6—C7—C8	130.6 (5)	C10—C11—H11	116.00
C7—C8—C9	131.7 (5)	C12—C11—H11	116.00
N4—C8—C9	124.8 (5)	C13—C14—H14	121.00
N4—C8—C7	103.5 (4)	C15—C14—H14	120.00
C8—C9—C10	128.3 (6)	C16—C15—H15	119.00
C9—C10—C11	121.9 (6)	C14—C15—H15	120.00
C10—C11—C12	127.3 (5)	C15—C16—H16	119.00
C11—C12—C13	131.5 (5)	C17—C16—H16	119.00
N5—C12—C11	125.5 (5)	C18—C17—H17	121.00
N5—C12—C13	102.9 (4)	C16—C17—H17	122.00
C12—C13—C14	130.6 (5)	Ni1—C001—N001	179.5 (5)
C14—C13—C18	119.4 (5)	Ni1—C002—N002	177.6 (5)
C12—C13—C18	110.0 (5)

C1—N1—N2—N3	−0.4 (6)	C1—C2—C3—C4	−178.7 (5)
C004—N1—N2—N3	175.9 (5)	C1—C2—C7—C6	178.7 (5)
N2—N1—C1—C2	179.5 (8)	C3—C2—C7—C6	0.3 (8)
N2—N1—C1—N4	0.3 (6)	C7—C2—C3—C4	−0.8 (7)
C004—N1—C1—N4	−175.6 (5)	C3—C2—C7—C8	180.0 (5)
C004—N1—C1—C2	3.6 (12)	C2—C3—C4—C5	1.0 (8)
N1—N2—N3—N4	0.4 (6)	C3—C4—C5—C6	−0.7 (9)
N2—N3—N4—C1	−0.3 (6)	C4—C5—C6—C7	0.1 (9)
N2—N3—N4—C8	−176.5 (6)	C5—C6—C7—C8	−179.5 (5)
C1—N4—C8—C9	−178.2 (5)	C5—C6—C7—C2	0.1 (8)
C1—N4—C8—C7	1.2 (6)	C2—C7—C8—C9	179.7 (6)
N3—N4—C8—C9	−2.0 (10)	C6—C7—C8—N4	180.0 (5)
C8—N4—C1—N1	177.2 (4)	C2—C7—C8—N4	0.3 (5)
N3—N4—C8—C7	177.4 (5)	C6—C7—C8—C9	−0.7 (10)
N3—N4—C1—N1	0.0 (6)	N4—C8—C9—C10	−0.5 (10)
N3—N4—C1—C2	−179.5 (4)	C7—C8—C9—C10	−179.8 (6)
C8—N4—C1—C2	−2.3 (6)	C8—C9—C10—C11	−178.8 (6)
C12—N5—N6—N7	−177.8 (6)	C9—C10—C11—C12	−179.7 (6)
N6—N5—C12—C13	174.9 (6)	C10—C11—C12—N5	1.5 (9)
C19—N5—C12—C13	−1.3 (6)	C10—C11—C12—C13	178.8 (6)
C12—N5—C19—C18	0.3 (6)	C11—C12—C13—C14	6.3 (10)
C12—N5—C19—N8	179.8 (4)	N5—C12—C13—C14	−175.9 (6)
C19—N5—N6—N7	−1.6 (6)	N5—C12—C13—C18	1.7 (6)
N6—N5—C19—N8	2.6 (6)	C11—C12—C13—C18	−176.1 (6)
N6—N5—C19—C18	−176.8 (4)	C14—C13—C18—C17	−0.4 (8)
C19—N5—C12—C11	176.7 (5)	C12—C13—C18—C19	−1.6 (6)
N6—N5—C12—C11	−7.2 (10)	C12—C13—C18—C17	−178.3 (5)
N5—N6—N7—N8	−0.1 (6)	C14—C13—C18—C19	176.3 (5)
N6—N7—N8—C003	179.0 (5)	C12—C13—C14—C15	177.3 (6)
N6—N7—N8—C19	1.8 (6)	C18—C13—C14—C15	−0.2 (8)
N7—N8—C19—N5	−2.7 (6)	C13—C14—C15—C16	1.0 (9)
C003—N8—C19—C18	−0.5 (13)	C14—C15—C16—C17	−1.3 (9)
C003—N8—C19—N5	−179.6 (5)	C15—C16—C17—C18	0.8 (9)
N7—N8—C19—C18	176.4 (8)	C16—C17—C18—C19	−175.6 (6)
N1—C1—C2—C3	1.4 (13)	C16—C17—C18—C13	0.1 (8)
N1—C1—C2—C7	−176.8 (8)	C13—C18—C19—N5	0.8 (6)
N4—C1—C2—C3	−179.4 (5)	C17—C18—C19—N8	−2.1 (14)
N4—C1—C2—C7	2.4 (6)	C13—C18—C19—N8	−178.3 (8)
C1—C2—C7—C8	−1.7 (6)	C17—C18—C19—N5	177.0 (6)

Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x−1, y−1, z−1; (v) x−1, y, z−1; (vi) x−1, y, z; (vii) −x+1/2, y−1/2, −z+1/2; (viii) −x+1, −y, −z; (ix) −x+2, −y, −z+1; (x) −x+2, −y+1, −z+1; (xi) x+1, y, z+1; (xii) x+1/2, −y+1/2, z+1/2; (xiii) x−3/2, −y+1/2, z−1/2; (xiv) x+1, y, z; (xv) x−1/2, −y+1/2, z−1/2; (xvi) −x+3/2, y−1/2, −z+3/2; (xvii) −x+3/2, y+1/2, −z+3/2; (xviii) −x+1/2, y+1/2, −z+1/2; (xix) x+1, y+1, z+1; (xx) −x+3/2, y−1/2, −z+1/2; (xxi) −x+2, −y+1, −z+2; (xxii) −x+3/2, y+1/2, −z+1/2; (xxiii) x+3/2, −y+1/2, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C003—H00E···N001ⁱⁱⁱ	0.96	2.59	3.532 (9)	166
C3—H3···N002^viii	0.98	2.54	3.509 (7)	171
C4—H4···N001^xiv	0.97	2.52	3.421 (7)	154
C004—H00A···N002^viii	0.96	2.49	3.394 (7)	157
C10—H10···N3	0.93	2.56	3.184 (8)	125
C10—H10···N6	0.93	2.56	3.193 (7)	126
C14—H14···N001^xviii	0.90	2.61	3.489 (7)	165

Symmetry codes: (iii) −x+1, −y+1, −z+1; (viii) −x+1, −y, −z; (xiv) x+1, y, z; (xviii) −x+1/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	(C₂₁H₁₇N₈)₂[Ni(CN)₄]
M_r	925.61
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	16.296 (2), 7.5708 (7), 18.537 (3)
β (°)	115.42 (2)
V (Å³)	2065.6 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.53
Crystal size (mm)	0.2 × 0.2 × 0.1

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan SORTAV (Blessing, 1995)
T_min, T_max	0.901, 0.949
No. of measured, independent and observed [I > 2σ(I)] reflections	18746, 4672, 3172
R_int	0.069
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.097, 0.176, 1.33
No. of reflections	4672
No. of parameters	314
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.73

Computer programs: Please provide, SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

Ni1—C001	1.868 (7)	N5—C19	1.352 (6)
Ni1—C002	1.888 (5)	N5—N6	1.371 (7)
N1—N2	1.371 (5)	N5—C12	1.415 (7)
N1—C004	1.462 (7)	N6—N7	1.290 (7)
N1—C1	1.344 (7)	N7—N8	1.353 (7)
N2—N3	1.297 (7)	N8—C003	1.463 (6)
N3—N4	1.364 (5)	N8—C19	1.344 (7)
N4—C1	1.352 (7)	N001—C001	1.160 (9)
N4—C8	1.407 (7)	N002—C002	1.148 (7)

C001—Ni1—C002	90.9 (2)	N6—N7—N8	109.5 (5)
C001—Ni1—C001ⁱ	180	N7—N8—C19	109.7 (4)
C001—Ni1—C002ⁱ	89.1 (2)	N7—N8—C003	121.8 (5)
C002—Ni1—C002ⁱ	180	C003—N8—C19	128.5 (5)
C1—N1—C004	130.0 (4)	N1—C1—C2	146.5 (5)
N2—N1—C1	109.4 (4)	N1—C1—N4	104.2 (4)
N2—N1—C004	120.5 (4)	N4—C1—C2	109.3 (5)
N1—N2—N3	108.9 (4)	N4—C8—C9	124.8 (5)
N2—N3—N4	106.5 (3)	N4—C8—C7	103.5 (4)
N3—N4—C8	137.0 (4)	N5—C12—C11	125.5 (5)
N3—N4—C1	111.0 (4)	N5—C12—C13	102.9 (4)
C1—N4—C8	112.0 (4)	N5—C19—C18	108.9 (5)
N6—N5—C12	136.9 (4)	N5—C19—N8	104.0 (4)
N6—N5—C19	110.5 (4)	N8—C19—C18	147.1 (5)
C12—N5—C19	112.5 (5)	Ni1—C001—N001	179.5 (5)
N5—N6—N7	106.2 (4)	Ni1—C002—N002	177.6 (5)

Symmetry code: (i) −x, −y, −z.