Synthesis, crystal structure, and Hirshfeld surface analysis of 3-ferrocenyl-1-(pyridin-2-yl)-1H-pyrazol-5-amine

The multi-step synthesis, characterization, and structural examination (single-crystal X-ray diffraction and Hirshfeld surface analysis) of 3-ferrocenyl-1-(pyridin-2-yl)-1H-pyrazol-5-amine (C₁₈H₁₆FeN₄), are reported. The supra­molecular characteristics, including π–π stacking and hydrogen bonding, are discussed, and a database exploration highlights the distinctive combination of mol­ecular components.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 110 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.036
• wR factor = 0.078
• Data-to-parameter ratio = 11.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -1.025 Report

Author Response: Small values for K are present only for the two weakest bins of Fc/Fc(max) (that is, 0.000 - 0.011 and 0.011 - 0.022). All other values range from 0.911 to 1.017.

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C18 H16 Fe1 N4
            Atom count from _chemical_formula_moiety:
PLAT794_ALERT_5_G Tentative Bond Valency for Fe1       (II)      .       2.12 Info
PLAT909_ALERT_3_G Percentage of I>2sig(I) Data at Theta(Max) Still        58% Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          3 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   2 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
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

Computing details

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2018); data reduction: SAINT (Bruker, 2018); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

3-Ferrocenyl-1-(pyridin-2-yl)-1H-pyrazol-5-amine

Crystal data

[Fe(C5H5)(C13H11N4)]	F(000) = 712
Mr = 344.20	Dx = 1.572 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.349 (8) Å	Cell parameters from 7455 reflections
b = 6.894 (3) Å	θ = 3.4–24.7°
c = 12.173 (5) Å	µ = 1.04 mm^−1
β = 92.878 (12)°	T = 110 K
V = 1454.0 (11) Å^3	Plate, orange
Z = 4	0.15 × 0.10 × 0.04 mm

Data collection

Bruker APEXII CCD diffractometer	1877 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.105
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θmax = 25.1°, θmin = 2.4°
Tmin = 0.829, Tmax = 0.956	h = −20→20
37974 measured reflections	k = −8→8
2578 independent reflections	l = −14→14

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.078	w = 1/[σ^2(Fo^2) + (0.0216P)^2 + 2.158P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
2578 reflections	Δρmax = 0.42 e Å^−3
216 parameters	Δρmin = −0.32 e Å^−3
0 restraints

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.

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

	x	y	z	Uiso*/Ueq
Fe1	0.13466 (2)	0.63057 (6)	0.39894 (3)	0.01773 (13)
N1	0.50809 (14)	0.3811 (4)	0.17719 (18)	0.0217 (6)
N2	0.38601 (13)	0.3858 (4)	0.24937 (18)	0.0175 (5)
N3	0.34008 (13)	0.3919 (4)	0.33927 (18)	0.0182 (5)
N4	0.37249 (17)	0.3811 (4)	0.0502 (2)	0.0232 (6)
H4A	0.3461 (18)	0.318 (5)	0.001 (3)	0.025 (9)*
H4B	0.423 (2)	0.378 (6)	0.054 (3)	0.047 (11)*
C1	0.58538 (17)	0.3775 (5)	0.1939 (2)	0.0249 (7)
H1	0.615939	0.377992	0.131304	0.030*
C2	0.62261 (17)	0.3733 (5)	0.2960 (2)	0.0266 (7)
H2	0.677358	0.370090	0.303644	0.032*
C3	0.57860 (17)	0.3738 (5)	0.3872 (2)	0.0248 (7)
H3	0.602776	0.371625	0.458937	0.030*
C4	0.49941 (16)	0.3774 (5)	0.3735 (2)	0.0220 (6)
H4	0.467917	0.377177	0.435100	0.026*
C5	0.46683 (16)	0.3813 (4)	0.2669 (2)	0.0162 (6)
C6	0.34133 (16)	0.3791 (4)	0.1515 (2)	0.0173 (6)
C7	0.26567 (16)	0.3809 (4)	0.1799 (2)	0.0195 (6)
H7	0.220986	0.377176	0.131562	0.023*
C8	0.26812 (16)	0.3896 (4)	0.2957 (2)	0.0169 (6)
C9	0.20262 (16)	0.3951 (4)	0.3665 (2)	0.0184 (6)
C10	0.12391 (16)	0.3580 (4)	0.3347 (2)	0.0205 (6)
H10	0.104586	0.326560	0.262506	0.025*
C11	0.07891 (17)	0.3757 (4)	0.4286 (2)	0.0206 (6)
H11	0.024704	0.357569	0.430408	0.025*
C12	0.12993 (17)	0.4254 (4)	0.5196 (2)	0.0201 (7)
H12	0.115721	0.445806	0.593091	0.024*
C13	0.20567 (17)	0.4393 (4)	0.4814 (2)	0.0191 (7)
H13	0.250783	0.472386	0.524847	0.023*
C14	0.16504 (19)	0.8494 (5)	0.2979 (3)	0.0344 (9)
H14	0.199240	0.838866	0.239615	0.041*
C15	0.08432 (19)	0.8210 (5)	0.2885 (3)	0.0313 (8)
H15	0.054821	0.787232	0.223430	0.038*
C16	0.05549 (18)	0.8521 (5)	0.3936 (3)	0.0272 (7)
H16	0.002936	0.844053	0.411569	0.033*
C17	0.11837 (18)	0.8970 (4)	0.4671 (3)	0.0293 (8)
H17	0.115362	0.923602	0.543339	0.035*
C18	0.18652 (19)	0.8960 (5)	0.4084 (3)	0.0347 (8)
H18	0.237283	0.921796	0.437669	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0171 (2)	0.0199 (2)	0.0163 (2)	0.0013 (2)	0.00189 (16)	0.0013 (2)
N1	0.0217 (14)	0.0254 (13)	0.0186 (13)	0.0004 (13)	0.0064 (11)	−0.0001 (13)
N2	0.0176 (13)	0.0225 (13)	0.0126 (11)	−0.0001 (12)	0.0015 (10)	0.0016 (12)
N3	0.0194 (13)	0.0231 (13)	0.0125 (12)	0.0038 (12)	0.0046 (10)	−0.0016 (11)
N4	0.0221 (16)	0.0333 (16)	0.0142 (13)	−0.0030 (14)	0.0029 (12)	−0.0051 (13)
C1	0.0211 (17)	0.0290 (17)	0.0254 (16)	−0.0003 (16)	0.0090 (13)	−0.0003 (16)
C2	0.0174 (16)	0.0306 (17)	0.0321 (18)	−0.0005 (16)	0.0043 (14)	−0.0026 (18)
C3	0.0237 (17)	0.0273 (16)	0.0229 (16)	−0.0036 (16)	−0.0017 (13)	0.0011 (16)
C4	0.0201 (16)	0.0288 (16)	0.0172 (15)	−0.0005 (16)	0.0027 (12)	0.0008 (16)
C5	0.0172 (15)	0.0133 (13)	0.0184 (14)	0.0009 (13)	0.0020 (12)	−0.0004 (14)
C6	0.0198 (16)	0.0181 (14)	0.0134 (14)	0.0009 (14)	−0.0027 (12)	−0.0009 (14)
C7	0.0203 (16)	0.0224 (15)	0.0153 (14)	0.0018 (15)	−0.0036 (12)	−0.0026 (14)
C8	0.0179 (15)	0.0167 (14)	0.0163 (14)	0.0014 (13)	0.0019 (12)	−0.0008 (13)
C9	0.0207 (16)	0.0178 (15)	0.0167 (15)	0.0007 (13)	0.0014 (12)	−0.0018 (13)
C10	0.0214 (16)	0.0225 (15)	0.0174 (15)	−0.0026 (15)	−0.0008 (12)	−0.0006 (14)
C11	0.0196 (16)	0.0214 (15)	0.0210 (15)	0.0004 (15)	0.0037 (12)	0.0023 (15)
C12	0.0239 (17)	0.0210 (16)	0.0155 (15)	0.0012 (13)	0.0037 (13)	0.0015 (12)
C13	0.0205 (17)	0.0206 (15)	0.0160 (15)	0.0016 (13)	−0.0001 (13)	−0.0013 (12)
C14	0.030 (2)	0.0301 (19)	0.045 (2)	0.0082 (16)	0.0199 (16)	0.0167 (18)
C15	0.0286 (19)	0.038 (2)	0.0273 (18)	0.0078 (16)	0.0037 (15)	0.0159 (15)
C16	0.0213 (17)	0.0259 (17)	0.0348 (18)	0.0042 (15)	0.0072 (14)	0.0088 (16)
C17	0.033 (2)	0.0200 (17)	0.0347 (18)	0.0048 (16)	0.0039 (16)	−0.0032 (15)
C18	0.0247 (18)	0.0235 (18)	0.056 (2)	−0.0034 (16)	0.0035 (17)	0.0041 (18)

Geometric parameters (Å, º)

Fe1—C14	2.033 (3)	C4—C5	1.389 (4)
Fe1—C13	2.035 (3)	C4—H4	0.9500
Fe1—C18	2.040 (3)	C6—C7	1.374 (4)
Fe1—C10	2.040 (3)	C7—C8	1.409 (4)
Fe1—C17	2.041 (3)	C7—H7	0.9500
Fe1—C15	2.044 (3)	C8—C9	1.460 (4)
Fe1—C12	2.044 (3)	C9—C10	1.423 (4)
Fe1—C11	2.047 (3)	C9—C13	1.431 (4)
Fe1—C16	2.053 (3)	C10—C11	1.422 (4)
Fe1—C9	2.056 (3)	C10—H10	0.9500
N1—C5	1.335 (3)	C11—C12	1.425 (4)
N1—C1	1.346 (4)	C11—H11	0.9500
N2—N3	1.386 (3)	C12—C13	1.419 (4)
N2—C6	1.389 (3)	C12—H12	0.9500
N2—C5	1.408 (3)	C13—H13	0.9500
N3—C8	1.332 (3)	C14—C15	1.413 (5)
N4—C6	1.371 (3)	C14—C18	1.415 (5)
N4—H4A	0.86 (3)	C14—H14	0.9500
N4—H4B	0.88 (4)	C15—C16	1.413 (4)
C1—C2	1.372 (4)	C15—H15	0.9500
C1—H1	0.9500	C16—C17	1.410 (4)
C2—C3	1.378 (4)	C16—H16	0.9500
C2—H2	0.9500	C17—C18	1.412 (5)
C3—C4	1.376 (4)	C17—H17	0.9500
C3—H3	0.9500	C18—H18	0.9500
C14—Fe1—C13	127.63 (13)	N4—C6—N2	122.9 (3)
C14—Fe1—C18	40.67 (14)	C7—C6—N2	106.4 (2)
C13—Fe1—C18	107.40 (13)	C6—C7—C8	105.7 (2)
C14—Fe1—C10	118.24 (13)	C6—C7—H7	127.1
C13—Fe1—C10	68.51 (12)	C8—C7—H7	127.1
C18—Fe1—C10	151.59 (13)	N3—C8—C7	112.3 (2)
C14—Fe1—C17	67.89 (14)	N3—C8—C9	120.4 (2)
C13—Fe1—C17	118.39 (13)	C7—C8—C9	127.3 (3)
C18—Fe1—C17	40.47 (13)	C10—C9—C13	107.0 (2)
C10—Fe1—C17	166.61 (12)	C10—C9—C8	126.8 (2)
C14—Fe1—C15	40.56 (13)	C13—C9—C8	126.2 (3)
C13—Fe1—C15	165.73 (12)	C10—C9—Fe1	69.06 (17)
C18—Fe1—C15	68.51 (14)	C13—C9—Fe1	68.72 (16)
C10—Fe1—C15	108.17 (13)	C8—C9—Fe1	127.2 (2)
C17—Fe1—C15	68.03 (14)	C11—C10—C9	108.9 (2)
C14—Fe1—C12	165.82 (13)	C11—C10—Fe1	69.90 (17)
C13—Fe1—C12	40.72 (11)	C9—C10—Fe1	70.27 (17)
C18—Fe1—C12	127.85 (14)	C11—C10—H10	125.5
C10—Fe1—C12	68.40 (12)	C9—C10—H10	125.5
C17—Fe1—C12	108.61 (13)	Fe1—C10—H10	125.9
C15—Fe1—C12	152.40 (13)	C10—C11—C12	107.5 (3)
C14—Fe1—C11	152.03 (13)	C10—C11—Fe1	69.39 (17)
C13—Fe1—C11	68.67 (12)	C12—C11—Fe1	69.50 (17)
C18—Fe1—C11	166.21 (13)	C10—C11—H11	126.2
C10—Fe1—C11	40.71 (11)	C12—C11—H11	126.2
C17—Fe1—C11	128.65 (12)	Fe1—C11—H11	126.4
C15—Fe1—C11	118.53 (13)	C13—C12—C11	108.1 (3)
C12—Fe1—C11	40.76 (11)	C13—C12—Fe1	69.30 (16)
C14—Fe1—C16	67.80 (13)	C11—C12—Fe1	69.74 (17)
C13—Fe1—C16	152.29 (12)	C13—C12—H12	125.9
C18—Fe1—C16	68.10 (14)	C11—C12—H12	125.9
C10—Fe1—C16	128.67 (12)	Fe1—C12—H12	126.6
C17—Fe1—C16	40.30 (12)	C12—C13—C9	108.5 (3)
C15—Fe1—C16	40.36 (12)	C12—C13—Fe1	69.99 (17)
C12—Fe1—C16	119.12 (12)	C9—C13—Fe1	70.34 (17)
C11—Fe1—C16	108.84 (13)	C12—C13—H13	125.8
C14—Fe1—C9	107.51 (13)	C9—C13—H13	125.8
C13—Fe1—C9	40.94 (11)	Fe1—C13—H13	125.5
C18—Fe1—C9	117.62 (13)	C15—C14—C18	108.7 (3)
C10—Fe1—C9	40.67 (11)	C15—C14—Fe1	70.14 (18)
C17—Fe1—C9	151.77 (12)	C18—C14—Fe1	69.94 (19)
C15—Fe1—C9	127.65 (12)	C15—C14—H14	125.6
C12—Fe1—C9	68.66 (11)	C18—C14—H14	125.6
C11—Fe1—C9	68.71 (12)	Fe1—C14—H14	125.9
C16—Fe1—C9	166.01 (12)	C14—C15—C16	107.5 (3)
C5—N1—C1	116.6 (2)	C14—C15—Fe1	69.30 (18)
N3—N2—C6	111.1 (2)	C16—C15—Fe1	70.17 (18)
N3—N2—C5	119.3 (2)	C14—C15—H15	126.3
C6—N2—C5	129.6 (2)	C16—C15—H15	126.3
C8—N3—N2	104.5 (2)	Fe1—C15—H15	125.8
C6—N4—H4A	114 (2)	C17—C16—C15	108.1 (3)
C6—N4—H4B	113 (2)	C17—C16—Fe1	69.41 (18)
H4A—N4—H4B	122 (3)	C15—C16—Fe1	69.47 (18)
N1—C1—C2	123.9 (3)	C17—C16—H16	126.0
N1—C1—H1	118.1	C15—C16—H16	126.0
C2—C1—H1	118.1	Fe1—C16—H16	126.7
C1—C2—C3	118.3 (3)	C16—C17—C18	108.6 (3)
C1—C2—H2	120.8	C16—C17—Fe1	70.29 (18)
C3—C2—H2	120.8	C18—C17—Fe1	69.71 (19)
C4—C3—C2	119.5 (3)	C16—C17—H17	125.7
C4—C3—H3	120.2	C18—C17—H17	125.7
C2—C3—H3	120.2	Fe1—C17—H17	125.9
C3—C4—C5	118.1 (3)	C17—C18—C14	107.2 (3)
C3—C4—H4	121.0	C17—C18—Fe1	69.82 (19)
C5—C4—H4	121.0	C14—C18—Fe1	69.39 (19)
N1—C5—C4	123.6 (3)	C17—C18—H18	126.4
N1—C5—N2	116.6 (2)	C14—C18—H18	126.4
C4—C5—N2	119.8 (2)	Fe1—C18—H18	125.9
N4—C6—C7	130.6 (3)
C6—N2—N3—C8	−0.2 (3)	Fe1—C9—C10—C11	−59.4 (2)
C5—N2—N3—C8	−178.3 (3)	C13—C9—C10—Fe1	58.5 (2)
C5—N1—C1—C2	0.3 (5)	C8—C9—C10—Fe1	−121.5 (3)
N1—C1—C2—C3	−0.4 (5)	C9—C10—C11—C12	0.4 (3)
C1—C2—C3—C4	0.4 (5)	Fe1—C10—C11—C12	−59.3 (2)
C2—C3—C4—C5	−0.3 (5)	C9—C10—C11—Fe1	59.6 (2)
C1—N1—C5—C4	−0.2 (5)	C10—C11—C12—C13	0.3 (3)
C1—N1—C5—N2	179.8 (3)	Fe1—C11—C12—C13	−58.9 (2)
C3—C4—C5—N1	0.2 (5)	C10—C11—C12—Fe1	59.2 (2)
C3—C4—C5—N2	−179.7 (3)	C11—C12—C13—C9	−0.9 (3)
N3—N2—C5—N1	−178.1 (2)	Fe1—C12—C13—C9	−60.1 (2)
C6—N2—C5—N1	4.1 (5)	C11—C12—C13—Fe1	59.1 (2)
N3—N2—C5—C4	1.8 (4)	C10—C9—C13—C12	1.1 (3)
C6—N2—C5—C4	−175.9 (3)	C8—C9—C13—C12	−178.9 (3)
N3—N2—C6—N4	177.0 (3)	Fe1—C9—C13—C12	59.8 (2)
C5—N2—C6—N4	−5.1 (5)	C10—C9—C13—Fe1	−58.7 (2)
N3—N2—C6—C7	0.0 (3)	C8—C9—C13—Fe1	121.3 (3)
C5—N2—C6—C7	177.9 (3)	C18—C14—C15—C16	0.6 (4)
N4—C6—C7—C8	−176.4 (3)	Fe1—C14—C15—C16	60.1 (2)
N2—C6—C7—C8	0.2 (3)	C18—C14—C15—Fe1	−59.5 (2)
N2—N3—C8—C7	0.4 (3)	C14—C15—C16—C17	−0.6 (4)
N2—N3—C8—C9	−179.8 (3)	Fe1—C15—C16—C17	58.9 (2)
C6—C7—C8—N3	−0.4 (4)	C14—C15—C16—Fe1	−59.5 (2)
C6—C7—C8—C9	179.8 (3)	C15—C16—C17—C18	0.5 (4)
N3—C8—C9—C10	−167.5 (3)	Fe1—C16—C17—C18	59.4 (2)
C7—C8—C9—C10	12.2 (5)	C15—C16—C17—Fe1	−58.9 (2)
N3—C8—C9—C13	12.5 (5)	C16—C17—C18—C14	−0.2 (4)
C7—C8—C9—C13	−167.7 (3)	Fe1—C17—C18—C14	59.6 (2)
N3—C8—C9—Fe1	102.0 (3)	C16—C17—C18—Fe1	−59.8 (2)
C7—C8—C9—Fe1	−78.2 (4)	C15—C14—C18—C17	−0.3 (4)
C13—C9—C10—C11	−0.9 (3)	Fe1—C14—C18—C17	−59.9 (2)
C8—C9—C10—C11	179.1 (3)	C15—C14—C18—Fe1	59.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N3^i	0.86 (3)	2.44 (3)	3.210 (4)	150 (3)
N4—H4B···N1	0.88 (4)	2.05 (4)	2.749 (4)	136 (3)

Symmetry code: (i) x, −y+1/2, z−1/2.