An iron(III) complex salt containing pyrazole as both ligand and counter-ion: bis­(1H-pyrazol-2-ium) penta­cyanido(1H-pyrazole-κN²)ferrate(III)

The title compound, (C₃H₅N₂)₂[Fe(CN)₅(C₃H₄N₂)], is com­posed of a mononuclear [Fe(CN)₅(pyrazole)]²⁻ dianion and two 1H-pyrazol-2-ium cations. A three-dimensional supra­molecular network is formed through a rich scheme of N—H...N hydrogen bonds and C—H...π inter­actions among the cations and anions.

Computing details

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: PLATON (Spek, 2009) and DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Bis(1H-pyrazol-2-ium) pentacyanido(1H-pyrazole-κN²)ferrate(III)

Crystal data

(C3H5N2)2[Fe(CN)5(C3H4N2)]	F(000) = 402
Mr = 392.21	Dx = 1.383 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 4324 reflections
a = 7.0219 (14) Å	θ = 3.2–27.5°
b = 14.955 (3) Å	µ = 0.82 mm^−1
c = 8.9722 (18) Å	T = 293 K
β = 91.19 (3)°	Block, red
V = 942.0 (3) Å^3	0.26 × 0.24 × 0.22 mm
Z = 2

Data collection

Rigaku SCXmini diffractometer	4054 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.039
Graphite monochromator	θmax = 27.5°, θmin = 3.2°
ω scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −19→19
Tmin = 0.807, Tmax = 0.834	l = −11→11
9783 measured reflections	3 standard reflections every 180 reflections
4324 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)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.071	w = 1/[σ^2(Fo^2) + (0.0227P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
4324 reflections	Δρmax = 0.30 e Å^−3
236 parameters	Δρmin = −0.36 e Å^−3
1 restraint	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.009 (13)

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
C1	0.9516 (3)	0.95613 (16)	0.8570 (3)	0.0307 (5)
C2	0.9554 (3)	0.97455 (15)	1.1628 (3)	0.0310 (5)
C3	0.6409 (3)	1.08628 (15)	1.1402 (3)	0.0299 (5)
C4	0.6405 (3)	1.06832 (15)	0.8337 (3)	0.0310 (5)
C5	0.9565 (3)	1.12400 (17)	0.9862 (3)	0.0303 (5)
C6	0.5295 (4)	0.77643 (18)	1.0404 (3)	0.0450 (7)
H6	0.5346	0.7146	1.0502	0.054*
C7	0.3672 (4)	0.82821 (17)	1.0342 (3)	0.0464 (7)
H7	0.2418	0.8086	1.0402	0.056*
C8	0.4288 (3)	0.91463 (17)	1.0174 (3)	0.0343 (5)
H8	0.3495	0.9643	1.0093	0.041*
C9	0.5215 (4)	0.8659 (2)	0.6366 (3)	0.0534 (7)
H9	0.5561	0.8472	0.7323	0.064*
C10	0.6429 (4)	0.8772 (2)	0.5213 (3)	0.0516 (7)
H10	0.7738	0.8677	0.5224	0.062*
C11	0.5324 (4)	0.9053 (2)	0.4051 (3)	0.0543 (8)
H11	0.5754	0.9194	0.3106	0.065*
C12	0.9262 (5)	0.6552 (3)	0.3973 (3)	0.0739 (11)
H12	0.9610	0.6497	0.2983	0.089*
C13	1.0434 (5)	0.6787 (3)	0.5125 (4)	0.0762 (10)
H13	1.1721	0.6930	0.5081	0.091*
C14	0.9350 (4)	0.6773 (2)	0.6350 (3)	0.0591 (8)
H14	0.9770	0.6903	0.7316	0.071*
Fe1	0.79424 (4)	1.02011 (2)	0.99859 (3)	0.02194 (8)
N1	1.0398 (3)	0.91860 (16)	0.7707 (2)	0.0475 (6)
N2	1.0465 (3)	0.94890 (17)	1.2607 (2)	0.0521 (6)
N3	0.5492 (3)	1.12183 (15)	1.2273 (2)	0.0476 (6)
N4	0.5522 (3)	1.09499 (16)	0.7347 (2)	0.0504 (6)
N5	1.0462 (3)	1.18743 (17)	0.9790 (2)	0.0476 (6)
N6	0.6206 (3)	0.91734 (11)	1.0142 (2)	0.0251 (4)
N7	0.6772 (3)	0.83135 (12)	1.0298 (2)	0.0326 (4)
H7A	0.7943	0.8144	1.0326	0.039*
N8	0.3536 (3)	0.90949 (16)	0.4477 (2)	0.0491 (6)
H8A	0.2577	0.9250	0.3924	0.059*
N9	0.3470 (3)	0.88577 (14)	0.5900 (2)	0.0417 (5)
H9A	0.2463	0.8837	0.6429	0.050*
N10	0.7598 (3)	0.65436 (15)	0.5955 (2)	0.0436 (5)
H10A	0.6656	0.6487	0.6545	0.052*
N11	0.7537 (3)	0.64151 (17)	0.4495 (3)	0.0504 (6)
H11A	0.6545	0.6267	0.3974	0.060*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0199 (11)	0.0425 (13)	0.0297 (13)	0.0028 (10)	0.0000 (9)	0.0059 (11)
C2	0.0223 (12)	0.0389 (13)	0.0318 (13)	0.0018 (9)	0.0024 (10)	0.0019 (10)
C3	0.0286 (12)	0.0309 (12)	0.0302 (12)	0.0014 (10)	0.0011 (10)	0.0039 (10)
C4	0.0309 (12)	0.0316 (12)	0.0307 (12)	0.0059 (9)	0.0039 (10)	−0.0011 (10)
C5	0.0281 (12)	0.0381 (13)	0.0249 (11)	−0.0012 (10)	0.0041 (9)	0.0010 (10)
C6	0.0480 (16)	0.0290 (13)	0.0579 (19)	−0.0109 (11)	0.0014 (13)	0.0062 (13)
C7	0.0273 (13)	0.0476 (16)	0.0646 (18)	−0.0121 (11)	0.0034 (12)	−0.0013 (14)
C8	0.0204 (11)	0.0372 (12)	0.0451 (14)	0.0008 (9)	0.0018 (10)	0.0009 (11)
C9	0.0505 (17)	0.081 (2)	0.0285 (13)	0.0213 (16)	−0.0103 (12)	−0.0020 (15)
C10	0.0292 (13)	0.076 (2)	0.0494 (16)	0.0093 (14)	−0.0009 (12)	−0.0045 (16)
C11	0.0451 (16)	0.078 (2)	0.0403 (15)	0.0045 (15)	0.0109 (13)	0.0148 (15)
C12	0.064 (2)	0.114 (3)	0.0445 (18)	−0.009 (2)	0.0196 (16)	−0.020 (2)
C13	0.0402 (18)	0.116 (3)	0.072 (2)	−0.0138 (19)	0.0062 (16)	0.003 (2)
C14	0.060 (2)	0.080 (2)	0.0361 (15)	−0.0054 (17)	−0.0171 (14)	0.0012 (16)
Fe1	0.01806 (13)	0.02601 (13)	0.02179 (13)	0.00165 (13)	0.00154 (9)	0.00192 (14)
N1	0.0339 (11)	0.0659 (15)	0.0429 (13)	0.0127 (11)	0.0072 (10)	−0.0077 (12)
N2	0.0412 (13)	0.0701 (16)	0.0445 (14)	0.0164 (12)	−0.0118 (11)	0.0126 (13)
N3	0.0514 (14)	0.0530 (14)	0.0389 (12)	0.0117 (11)	0.0137 (10)	−0.0031 (11)
N4	0.0531 (15)	0.0545 (14)	0.0432 (13)	0.0156 (11)	−0.0112 (11)	0.0045 (12)
N5	0.0458 (13)	0.0538 (14)	0.0435 (12)	−0.0170 (12)	0.0047 (10)	0.0016 (11)
N6	0.0223 (9)	0.0239 (9)	0.0292 (9)	0.0034 (7)	0.0023 (7)	0.0028 (8)
N7	0.0276 (10)	0.0271 (10)	0.0429 (11)	0.0050 (8)	−0.0009 (8)	0.0020 (8)
N8	0.0410 (13)	0.0675 (16)	0.0385 (13)	0.0147 (12)	−0.0074 (11)	0.0113 (12)
N9	0.0394 (13)	0.0527 (14)	0.0333 (12)	0.0081 (11)	0.0091 (10)	−0.0030 (11)
N10	0.0421 (13)	0.0559 (14)	0.0333 (12)	−0.0034 (11)	0.0110 (10)	0.0049 (11)
N11	0.0439 (14)	0.0671 (16)	0.0398 (13)	−0.0142 (12)	−0.0086 (11)	−0.0080 (13)

Geometric parameters (Å, º)

C1—N1	1.148 (3)	C10—C11	1.353 (4)
C1—Fe1	1.951 (2)	C10—H10	0.9300
C2—N2	1.142 (3)	C11—N8	1.322 (3)
C2—Fe1	1.961 (2)	C11—H11	0.9300
C3—N3	1.153 (3)	C12—N11	1.324 (4)
C3—Fe1	1.952 (2)	C12—C13	1.354 (4)
C4—N4	1.145 (3)	C12—H12	0.9300
C4—Fe1	1.951 (2)	C13—C14	1.350 (4)
C5—N5	1.141 (3)	C13—H13	0.9300
C5—Fe1	1.931 (3)	C14—N10	1.318 (3)
C6—N7	1.328 (3)	C14—H14	0.9300
C6—C7	1.378 (4)	Fe1—N6	1.9686 (18)
C6—H6	0.9300	N6—N7	1.352 (2)
C7—C8	1.372 (3)	N7—H7A	0.8600
C7—H7	0.9300	N8—N9	1.327 (3)
C8—N6	1.348 (3)	N8—H8A	0.8600
C8—H8	0.9300	N9—H9A	0.8600
C9—N9	1.321 (3)	N10—N11	1.324 (3)
C9—C10	1.364 (4)	N10—H10A	0.8600
C9—H9	0.9300	N11—H11A	0.8600
N1—C1—Fe1	178.0 (2)	C5—Fe1—C1	90.82 (10)
N2—C2—Fe1	178.4 (2)	C4—Fe1—C1	89.97 (9)
N3—C3—Fe1	176.9 (2)	C5—Fe1—C3	87.91 (10)
N4—C4—Fe1	178.3 (2)	C4—Fe1—C3	90.11 (9)
N5—C5—Fe1	177.4 (2)	C1—Fe1—C3	178.72 (11)
N7—C6—C7	107.2 (2)	C5—Fe1—C2	89.48 (10)
N7—C6—H6	126.4	C4—Fe1—C2	178.10 (11)
C7—C6—H6	126.4	C1—Fe1—C2	89.60 (9)
C8—C7—C6	105.7 (2)	C3—Fe1—C2	90.28 (10)
C8—C7—H7	127.1	C5—Fe1—N6	177.68 (10)
C6—C7—H7	127.1	C4—Fe1—N6	90.50 (9)
N6—C8—C7	110.4 (2)	C1—Fe1—N6	91.35 (9)
N6—C8—H8	124.8	C3—Fe1—N6	89.92 (9)
C7—C8—H8	124.8	C2—Fe1—N6	91.36 (9)
N9—C9—C10	108.8 (2)	C8—N6—N7	105.13 (18)
N9—C9—H9	125.6	C8—N6—Fe1	130.19 (15)
C10—C9—H9	125.6	N7—N6—Fe1	124.64 (14)
C11—C10—C9	105.4 (2)	C6—N7—N6	111.5 (2)
C11—C10—H10	127.3	C6—N7—H7A	124.2
C9—C10—H10	127.3	N6—N7—H7A	124.2
N8—C11—C10	109.0 (2)	C11—N8—N9	108.5 (2)
N8—C11—H11	125.5	C11—N8—H8A	125.7
C10—C11—H11	125.5	N9—N8—H8A	125.7
N11—C12—C13	108.4 (3)	C9—N9—N8	108.3 (2)
N11—C12—H12	125.8	C9—N9—H9A	125.9
C13—C12—H12	125.8	N8—N9—H9A	125.9
C14—C13—C12	105.8 (3)	C14—N10—N11	108.3 (2)
C14—C13—H13	127.1	C14—N10—H10A	125.8
C12—C13—H13	127.1	N11—N10—H10A	125.8
N10—C14—C13	108.9 (3)	C12—N11—N10	108.5 (2)
N10—C14—H14	125.5	C12—N11—H11A	125.8
C13—C14—H14	125.5	N10—N11—H11A	125.8
C5—Fe1—C4	88.67 (10)
N7—C6—C7—C8	0.9 (3)	N2—C2—Fe1—C5	94 (9)
C6—C7—C8—N6	−0.4 (3)	N2—C2—Fe1—C4	108 (9)
N9—C9—C10—C11	0.4 (4)	N2—C2—Fe1—C1	−175 (100)
C9—C10—C11—N8	−0.8 (4)	N2—C2—Fe1—C3	6 (9)
N11—C12—C13—C14	0.8 (5)	N2—C2—Fe1—N6	−84 (9)
C12—C13—C14—N10	−0.3 (4)	C7—C8—N6—N7	−0.2 (3)
N5—C5—Fe1—C4	51 (5)	C7—C8—N6—Fe1	−178.04 (18)
N5—C5—Fe1—C1	140 (5)	C5—Fe1—N6—C8	21 (2)
N5—C5—Fe1—C3	−40 (5)	C4—Fe1—N6—C8	−47.5 (2)
N5—C5—Fe1—C2	−130 (5)	C1—Fe1—N6—C8	−137.5 (2)
N5—C5—Fe1—N6	−19 (7)	C3—Fe1—N6—C8	42.6 (2)
N4—C4—Fe1—C5	106 (8)	C2—Fe1—N6—C8	132.9 (2)
N4—C4—Fe1—C1	16 (8)	C5—Fe1—N6—N7	−156 (2)
N4—C4—Fe1—C3	−166 (8)	C4—Fe1—N6—N7	135.01 (18)
N4—C4—Fe1—C2	92 (9)	C1—Fe1—N6—N7	45.02 (18)
N4—C4—Fe1—N6	−76 (8)	C3—Fe1—N6—N7	−134.88 (18)
N1—C1—Fe1—C5	−112 (6)	C2—Fe1—N6—N7	−44.60 (18)
N1—C1—Fe1—C4	−23 (6)	C7—C6—N7—N6	−1.1 (3)
N1—C1—Fe1—C3	−117 (7)	C8—N6—N7—C6	0.8 (3)
N1—C1—Fe1—C2	159 (6)	Fe1—N6—N7—C6	178.79 (16)
N1—C1—Fe1—N6	67 (6)	C10—C11—N8—N9	0.8 (4)
N3—C3—Fe1—C5	−143 (4)	C10—C9—N9—N8	0.1 (4)
N3—C3—Fe1—C4	128 (4)	C11—N8—N9—C9	−0.6 (3)
N3—C3—Fe1—C1	−138 (5)	C13—C14—N10—N11	−0.3 (4)
N3—C3—Fe1—C2	−53 (4)	C13—C12—N11—N10	−1.0 (4)
N3—C3—Fe1—N6	38 (4)	C14—N10—N11—C12	0.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7A···N5^i	0.86	2.21	2.901 (3)	138
N8—H8A···N2^ii	0.86	1.91	2.768 (3)	175
N9—H9A···N1^iii	0.86	1.94	2.769 (3)	162
N10—H10A···N3^iv	0.86	1.90	2.760 (3)	173
N11—H11A···N4^v	0.86	1.91	2.771 (3)	175

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