Crystal structure and Hirshfeld surface analysis of di­chlorido­tetra­kis­(4-methyl-1H-pyrazole-κN²)nickel(II) aceto­nitrile disolvate

The synthesis and crystal structure of the title mononuclear pyrazole-based complex, [Ni(C₄H₆N₂)₄Cl₂]·2CH₃CN, are reported along with the results of a Hirshfeld surface analysis.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.047
• wR factor = 0.130
• Data-to-parameter ratio = 20.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT601_ALERT_2_C Unit Cell Contains Solvent Accessible VOIDS of .         35 Ang   3
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.298 Check

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT480_ALERT_4_G Long H...A H-Bond Reported H10C     ..CL1      .       2.94 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H10B     ..CL1      .       3.12 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H5       ..N5       .       2.74 Ang.
PLAT794_ALERT_5_G Tentative Bond Valency for Ni1       (II)      .       1.96 Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        675 Note
PLAT933_ALERT_2_G Number of HKL-OMIT Records in Embedded .res File          1 Note
PLAT941_ALERT_3_G Average HKL Measurement Multiplicity ...........        1.7 Low
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          1 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
  11 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2021); cell refinement: CrysAlis PRO (Rigaku OD, 2021); data reduction: CrysAlis PRO (Rigaku OD, 2021); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Dichloridotetrakis(4-methyl-1H-pyrazole-κN²)nickel(II) acetonitrile disolvate

Crystal data

[NiCl2(C4H6N2)4]·2C2H3N	Z = 1
Mr = 540.15	F(000) = 282
Triclinic, P1	Dx = 1.296 Mg m^−3
a = 6.9625 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.8482 (8) Å	Cell parameters from 1586 reflections
c = 11.0920 (12) Å	θ = 2.3–29.1°
α = 74.417 (8)°	µ = 0.92 mm^−1
β = 81.495 (6)°	T = 293 K
γ = 71.191 (6)°	Plate, clear light blue
V = 691.92 (10) Å^3	0.2 × 0.15 × 0.03 mm

Data collection

Xcalibur, Eos diffractometer	3161 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2500 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
Detector resolution: 16.1593 pixels mm^-1	θmax = 29.4°, θmin = 1.9°
ω scans	h = −8→9
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2021)	k = −13→12
Tmin = 0.795, Tmax = 1.000	l = −14→15
5491 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.130	w = 1/[σ^2(Fo^2) + (0.0597P)^2 + 0.1286P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
3161 reflections	Δρmax = 0.57 e Å^−3
154 parameters	Δρmin = −0.45 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
Ni1	0.500000	0.500000	1.000000	0.03038 (17)
C3	0.7595 (4)	0.6698 (3)	0.7894 (3)	0.0418 (7)
H3	0.885178	0.600521	0.807503	0.050*
N2	0.4458 (4)	0.7836 (3)	0.7985 (2)	0.0433 (6)
H2	0.318650	0.807118	0.822630	0.052*
N3	0.4456 (3)	0.4131 (2)	0.8602 (2)	0.0357 (5)
C5	0.2833 (5)	0.3210 (4)	0.7604 (3)	0.0509 (8)
H5	0.184629	0.285430	0.742681	0.061*
C2	0.7297 (5)	0.7927 (4)	0.6882 (3)	0.0451 (7)
C7	0.5519 (4)	0.3886 (3)	0.7546 (3)	0.0423 (7)
H7	0.676277	0.406895	0.728729	0.051*
C6	0.4560 (5)	0.3325 (3)	0.6874 (3)	0.0464 (7)
C1	0.5283 (5)	0.8623 (4)	0.6981 (3)	0.0522 (8)
H1	0.458925	0.949441	0.644659	0.063*
C8	0.5300 (7)	0.2883 (5)	0.5643 (4)	0.0789 (12)
H8A	0.602413	0.184814	0.580475	0.118*
H8B	0.618933	0.343879	0.517855	0.118*
H8C	0.415733	0.308009	0.516557	0.118*
N1	0.5870 (3)	0.6636 (2)	0.8565 (2)	0.0354 (5)
Cl1	0.14603 (9)	0.65951 (7)	0.99696 (7)	0.0397 (2)
N4	0.2819 (3)	0.3701 (3)	0.8618 (3)	0.0433 (6)
H4	0.186829	0.373560	0.921075	0.052*
C4	0.8908 (6)	0.8343 (5)	0.5915 (4)	0.0752 (12)
H4A	1.021370	0.791110	0.626254	0.113*
H4B	0.861116	0.939785	0.568022	0.113*
H4C	0.892391	0.798492	0.518891	0.113*
C9	0.9065 (6)	0.0384 (4)	0.8290 (4)	0.0599 (9)
N5	1.0344 (5)	0.0551 (4)	0.7595 (4)	0.0803 (11)
C10	0.7409 (5)	0.0148 (4)	0.9202 (4)	0.0674 (11)
H10A	0.620906	0.035123	0.877485	0.101*
H10B	0.714797	0.079430	0.975807	0.101*
H10C	0.777646	−0.085902	0.967767	0.101*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0233 (2)	0.0330 (3)	0.0342 (3)	−0.01078 (19)	0.00342 (19)	−0.0069 (2)
C3	0.0322 (14)	0.0492 (18)	0.0462 (18)	−0.0196 (13)	0.0066 (13)	−0.0110 (15)
N2	0.0338 (12)	0.0407 (15)	0.0471 (15)	−0.0084 (11)	0.0012 (11)	−0.0019 (12)
N3	0.0285 (11)	0.0391 (13)	0.0412 (14)	−0.0139 (10)	0.0028 (10)	−0.0105 (11)
C5	0.0442 (17)	0.057 (2)	0.061 (2)	−0.0219 (15)	−0.0078 (16)	−0.0199 (17)
C2	0.0520 (18)	0.056 (2)	0.0330 (16)	−0.0293 (16)	0.0077 (14)	−0.0092 (14)
C7	0.0400 (15)	0.0505 (18)	0.0417 (17)	−0.0208 (13)	0.0078 (13)	−0.0160 (14)
C6	0.0565 (19)	0.0449 (19)	0.0390 (17)	−0.0168 (15)	−0.0018 (14)	−0.0104 (14)
C1	0.057 (2)	0.052 (2)	0.0391 (18)	−0.0174 (16)	−0.0001 (15)	0.0031 (15)
C8	0.109 (3)	0.085 (3)	0.056 (3)	−0.038 (3)	0.008 (2)	−0.034 (2)
N1	0.0320 (11)	0.0358 (13)	0.0383 (13)	−0.0136 (10)	0.0027 (10)	−0.0072 (11)
Cl1	0.0231 (3)	0.0415 (4)	0.0513 (5)	−0.0089 (3)	0.0037 (3)	−0.0101 (3)
N4	0.0299 (12)	0.0513 (15)	0.0537 (16)	−0.0178 (11)	0.0060 (11)	−0.0181 (13)
C4	0.079 (3)	0.092 (3)	0.056 (2)	−0.047 (2)	0.023 (2)	−0.007 (2)
C9	0.057 (2)	0.052 (2)	0.067 (3)	−0.0080 (17)	−0.011 (2)	−0.0142 (19)
N5	0.066 (2)	0.081 (3)	0.091 (3)	−0.0224 (18)	0.009 (2)	−0.022 (2)
C10	0.059 (2)	0.065 (3)	0.071 (3)	−0.0125 (19)	−0.002 (2)	−0.014 (2)

Geometric parameters (Å, º)

Ni1—N3	2.091 (2)	C2—C4	1.511 (4)
Ni1—N3^i	2.092 (2)	C7—H7	0.9300
Ni1—N1	2.112 (2)	C7—C6	1.383 (4)
Ni1—N1^i	2.112 (2)	C6—C8	1.512 (5)
Ni1—Cl1^i	2.4581 (6)	C1—H1	0.9300
Ni1—Cl1	2.4581 (6)	C8—H8A	0.9600
C3—H3	0.9300	C8—H8B	0.9600
C3—C2	1.394 (4)	C8—H8C	0.9600
C3—N1	1.326 (3)	N4—H4	0.8600
N2—H2	0.8600	C4—H4A	0.9600
N2—C1	1.344 (4)	C4—H4B	0.9600
N2—N1	1.345 (3)	C4—H4C	0.9600
N3—C7	1.327 (4)	C9—N5	1.113 (5)
N3—N4	1.334 (3)	C9—C10	1.452 (5)
C5—H5	0.9300	C10—H10A	0.9600
C5—C6	1.365 (4)	C10—H10B	0.9600
C5—N4	1.337 (4)	C10—H10C	0.9600
C2—C1	1.350 (5)
N3—Ni1—N3^i	180.0	C6—C7—H7	124.0
N3^i—Ni1—N1^i	88.18 (9)	C5—C6—C7	104.0 (3)
N3^i—Ni1—N1	91.82 (9)	C5—C6—C8	128.1 (3)
N3—Ni1—N1^i	91.83 (9)	C7—C6—C8	127.9 (3)
N3—Ni1—N1	88.17 (9)	N2—C1—C2	108.0 (3)
N3^i—Ni1—Cl1^i	89.43 (6)	N2—C1—H1	126.0
N3^i—Ni1—Cl1	90.57 (6)	C2—C1—H1	126.0
N3—Ni1—Cl1	89.43 (6)	C6—C8—H8A	109.5
N3—Ni1—Cl1^i	90.57 (6)	C6—C8—H8B	109.5
N1^i—Ni1—N1	180.0	C6—C8—H8C	109.5
N1—Ni1—Cl1	89.91 (6)	H8A—C8—H8B	109.5
N1^i—Ni1—Cl1	90.09 (6)	H8A—C8—H8C	109.5
N1—Ni1—Cl1^i	90.09 (6)	H8B—C8—H8C	109.5
N1^i—Ni1—Cl1^i	89.91 (6)	C3—N1—Ni1	134.1 (2)
Cl1^i—Ni1—Cl1	180.0	C3—N1—N2	104.4 (2)
C2—C3—H3	124.1	N2—N1—Ni1	120.53 (17)
N1—C3—H3	124.1	N3—N4—C5	111.9 (3)
N1—C3—C2	111.8 (3)	N3—N4—H4	124.0
C1—N2—H2	124.3	C5—N4—H4	124.0
C1—N2—N1	111.4 (2)	C2—C4—H4A	109.5
N1—N2—H2	124.3	C2—C4—H4B	109.5
C7—N3—Ni1	131.41 (19)	C2—C4—H4C	109.5
C7—N3—N4	104.5 (2)	H4A—C4—H4B	109.5
N4—N3—Ni1	124.12 (18)	H4A—C4—H4C	109.5
C6—C5—H5	126.2	H4B—C4—H4C	109.5
N4—C5—H5	126.2	N5—C9—C10	179.3 (5)
N4—C5—C6	107.6 (3)	C9—C10—H10A	109.5
C3—C2—C4	126.4 (3)	C9—C10—H10B	109.5
C1—C2—C3	104.3 (3)	C9—C10—H10C	109.5
C1—C2—C4	129.3 (3)	H10A—C10—H10B	109.5
N3—C7—H7	124.0	H10A—C10—H10C	109.5
N3—C7—C6	112.1 (3)	H10B—C10—H10C	109.5
Ni1—N3—C7—C6	−178.4 (2)	C1—N2—N1—Ni1	−170.4 (2)
Ni1—N3—N4—C5	179.1 (2)	C1—N2—N1—C3	0.0 (3)
C3—C2—C1—N2	−0.5 (4)	N1—C3—C2—C1	0.5 (4)
N3—C7—C6—C5	−1.2 (4)	N1—C3—C2—C4	−179.4 (3)
N3—C7—C6—C8	−178.9 (3)	N1—N2—C1—C2	0.3 (4)
C2—C3—N1—Ni1	168.1 (2)	N4—N3—C7—C6	1.0 (3)
C2—C3—N1—N2	−0.3 (3)	N4—C5—C6—C7	0.8 (4)
C7—N3—N4—C5	−0.5 (3)	N4—C5—C6—C8	178.5 (3)
C6—C5—N4—N3	−0.3 (4)	C4—C2—C1—N2	179.4 (3)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N5^ii	0.86	2.60	3.217 (4)	130
C10^ii—H10C^ii···Cl1	0.96	2.94	3.697 (3)	137
N2—H2···Cl1	0.86	2.50	3.088 (3)	127
N4—H4···Cl1^iii	0.86	2.45	3.217 (2)	149
C10^i—H10B^i···Cl1	0.96	3.12	3.8958 (3)	139
C5—H5···N5^iv	0.93	2.74	3.5785 (2)	150

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