Synthesis, crystal structure and Hirshfeld and thermal analysis of bis[benzyl 2-(heptan-4-yl­idene)hydrazine-1-carboxyl­ate-κ²N²,O]bis(thio­cyanato)­nickel(II)

The mol­ecular and crystal structure of bis­[benzyl 2-(heptan-4-yl­idene)hydrazine-1-carboxyl­ate-κ²N²,O]bis­(thio­cyanato)­nickel(II) is reported. Hirshfeld surface and simultaneous TGA–DTA analyses are also described

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.031
• wR factor = 0.073
• Data-to-parameter ratio = 21.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H8       ..S1       .       2.94 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H10A     ..S1       .       3.00 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H10B     ..S1       .       2.94 Ang.
PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of .         88 Ang   3
PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Theta(Min).          6 Note
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          2 Report

Alert level G
PLAT230_ALERT_2_G Hirshfeld Test Diff for    S1       --C16      .       10.4 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Ni1      --N1       .        6.2 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Ni1      --N3       .        5.8 s.u.
PLAT794_ALERT_5_G Tentative Bond Valency for Ni1       (II)      .       2.09 Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        766 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          1 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         11 Info

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 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
   4 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

Computing details

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/1 (Sheldrick, 2015b) and TITAN (Hunter & Simpson, 1999); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: SHELXL2018/1 (Sheldrick, 2015b), enCIFer (Allen et al., 2004), PLATON (Spek, 2020) and publCIF (Westrip 2010).

Bis[benzyl 2-(heptan-4-ylidene)hydrazine-1-carboxylate-κ²N²,O]bis(thiocyanato)nickel(II)

Crystal data

[Ni(NCS)2(C15H22N2O2)2]	F(000) = 740
Mr = 699.56	Dx = 1.216 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.6406 (3) Å	Cell parameters from 6613 reflections
b = 10.1280 (3) Å	θ = 3.6–29.2°
c = 15.7458 (4) Å	µ = 0.66 mm^−1
β = 108.647 (3)°	T = 100 K
V = 1910.02 (9) Å^3	Rectangular block, blue
Z = 2	0.39 × 0.24 × 0.16 mm

Data collection

Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer	4575 independent reflections
Radiation source: Agilent SuperNova (Mo) X-ray Source	3961 reflections with I > 2σ(I)
Detector resolution: 5.1725 pixels mm^-1	Rint = 0.027
ω scans	θmax = 29.6°, θmin = 3.2°
Absorption correction: multi-scan (CrysAlisPro; Agilent, 2014)	h = −17→17
Tmin = 0.772, Tmax = 1.000	k = −13→13
12439 measured reflections	l = −21→21

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.073	w = 1/[σ^2(Fo^2) + (0.0259P)^2 + 0.7321P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
4575 reflections	Δρmax = 0.33 e Å^−3
210 parameters	Δρmin = −0.38 e Å^−3

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.

Refinement. One reflection with Fo >>> Fc was omitted from the final refinement cycles.

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

	x	y	z	Uiso*/Ueq
Ni1	0.500000	0.000000	1.000000	0.01311 (7)
O1	0.34390 (7)	0.04585 (10)	1.01346 (6)	0.0166 (2)
C1	0.33197 (11)	−0.01165 (14)	1.07823 (9)	0.0159 (3)
O2	0.25009 (8)	0.01215 (11)	1.11267 (7)	0.0210 (2)
C2	0.16396 (11)	0.10284 (16)	1.06322 (10)	0.0208 (3)
H2A	0.137728	0.078992	0.998872	0.025*
H2B	0.193675	0.194018	1.069115	0.025*
C3	0.06895 (11)	0.09413 (16)	1.10129 (10)	0.0207 (3)
C4	−0.00906 (14)	0.19554 (19)	1.08242 (13)	0.0357 (4)
H4	−0.000374	0.268997	1.047719	0.043*
C5	−0.09990 (15)	0.1901 (2)	1.11410 (14)	0.0428 (5)
H5	−0.153094	0.259680	1.100762	0.051*
C6	−0.11294 (13)	0.0844 (2)	1.16464 (12)	0.0338 (4)
H6	−0.174835	0.081002	1.186420	0.041*
C7	−0.03610 (13)	−0.01634 (18)	1.18350 (11)	0.0277 (4)
H7	−0.044911	−0.089213	1.218626	0.033*
C8	0.05482 (12)	−0.01236 (16)	1.15143 (10)	0.0226 (3)
H8	0.107027	−0.082965	1.164090	0.027*
N2	0.39863 (10)	−0.10797 (13)	1.12383 (8)	0.0187 (3)
H2N	0.3879 (13)	−0.1414 (17)	1.1681 (12)	0.022*
N1	0.48528 (9)	−0.14754 (12)	1.09226 (8)	0.0156 (2)
C9	0.52823 (11)	−0.26137 (15)	1.11779 (9)	0.0170 (3)
C10	0.48835 (12)	−0.35599 (15)	1.17505 (10)	0.0194 (3)
H10A	0.470958	−0.306629	1.223216	0.023*
H10B	0.548117	−0.420395	1.203426	0.023*
C11	0.38364 (14)	−0.42957 (18)	1.11758 (11)	0.0308 (4)
H11A	0.321679	−0.365719	1.094963	0.037*
H11B	0.398761	−0.469318	1.065186	0.037*
C12	0.34816 (16)	−0.53771 (19)	1.17007 (13)	0.0375 (4)
H12A	0.406779	−0.605036	1.188334	0.056*
H12B	0.278687	−0.578254	1.132223	0.056*
H12C	0.336205	−0.499402	1.223428	0.056*
C13	0.62074 (12)	−0.30822 (16)	1.08489 (10)	0.0209 (3)
H13A	0.618840	−0.257813	1.030547	0.025*
H13B	0.608894	−0.402577	1.068126	0.025*
C14	0.73513 (12)	−0.29144 (18)	1.15569 (12)	0.0290 (4)
H14A	0.734359	−0.332963	1.212408	0.035*
H14B	0.751004	−0.196209	1.167194	0.035*
C15	0.82738 (14)	−0.3542 (2)	1.12562 (14)	0.0391 (5)
H15A	0.814383	−0.449445	1.117866	0.059*
H15B	0.899948	−0.338260	1.171121	0.059*
H15C	0.826912	−0.314947	1.068597	0.059*
N3	0.57102 (10)	0.12673 (13)	1.09988 (8)	0.0189 (3)
C16	0.61615 (11)	0.21720 (15)	1.14054 (9)	0.0162 (3)
S1	0.68148 (3)	0.34303 (4)	1.19984 (3)	0.02219 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01222 (12)	0.01537 (14)	0.01307 (13)	−0.00022 (9)	0.00589 (10)	−0.00050 (10)
O1	0.0141 (4)	0.0200 (5)	0.0175 (5)	0.0017 (4)	0.0076 (4)	0.0030 (4)
C1	0.0132 (6)	0.0193 (8)	0.0164 (7)	−0.0004 (5)	0.0066 (5)	−0.0015 (6)
O2	0.0172 (5)	0.0278 (6)	0.0224 (5)	0.0092 (4)	0.0126 (4)	0.0091 (4)
C2	0.0168 (7)	0.0233 (8)	0.0227 (7)	0.0063 (6)	0.0069 (6)	0.0052 (6)
C3	0.0163 (7)	0.0258 (9)	0.0207 (7)	0.0031 (6)	0.0071 (6)	−0.0024 (6)
C4	0.0322 (9)	0.0337 (11)	0.0487 (11)	0.0130 (8)	0.0233 (8)	0.0116 (9)
C5	0.0314 (9)	0.0460 (12)	0.0597 (13)	0.0201 (9)	0.0269 (9)	0.0074 (10)
C6	0.0204 (8)	0.0495 (12)	0.0376 (9)	0.0033 (8)	0.0177 (7)	−0.0030 (9)
C7	0.0189 (7)	0.0404 (11)	0.0251 (8)	−0.0020 (7)	0.0087 (7)	0.0017 (7)
C8	0.0147 (7)	0.0306 (9)	0.0229 (8)	0.0023 (6)	0.0066 (6)	0.0004 (7)
N2	0.0181 (6)	0.0228 (7)	0.0201 (6)	0.0053 (5)	0.0128 (5)	0.0060 (5)
N1	0.0134 (5)	0.0196 (7)	0.0161 (6)	0.0022 (5)	0.0081 (5)	−0.0003 (5)
C9	0.0167 (6)	0.0184 (8)	0.0164 (6)	−0.0002 (6)	0.0060 (5)	−0.0006 (6)
C10	0.0228 (7)	0.0173 (8)	0.0209 (7)	0.0022 (6)	0.0109 (6)	0.0010 (6)
C11	0.0372 (9)	0.0278 (10)	0.0280 (8)	−0.0102 (7)	0.0110 (7)	−0.0019 (7)
C12	0.0428 (10)	0.0303 (10)	0.0407 (10)	−0.0142 (8)	0.0154 (9)	−0.0007 (8)
C13	0.0241 (7)	0.0185 (8)	0.0244 (7)	0.0047 (6)	0.0139 (6)	0.0030 (6)
C14	0.0216 (7)	0.0288 (10)	0.0385 (9)	0.0033 (7)	0.0124 (7)	0.0056 (8)
C15	0.0280 (8)	0.0395 (11)	0.0571 (12)	0.0144 (8)	0.0237 (9)	0.0214 (9)
N3	0.0196 (6)	0.0213 (7)	0.0167 (6)	−0.0013 (5)	0.0072 (5)	−0.0016 (5)
C16	0.0157 (6)	0.0195 (8)	0.0162 (6)	0.0031 (6)	0.0090 (5)	0.0028 (6)
S1	0.02393 (19)	0.0196 (2)	0.0279 (2)	−0.00579 (15)	0.01512 (16)	−0.00852 (16)

Geometric parameters (Å, º)

Ni1—N3	2.0059 (13)	N2—H2N	0.824 (17)
Ni1—N3^i	2.0059 (12)	N1—C9	1.2829 (19)
Ni1—O1^i	2.1028 (9)	C9—C13	1.4994 (18)
Ni1—O1	2.1028 (9)	C9—C10	1.5086 (19)
Ni1—N1^i	2.1332 (12)	C10—C11	1.536 (2)
Ni1—N1	2.1332 (12)	C10—H10A	0.9900
O1—C1	1.2249 (17)	C10—H10B	0.9900
C1—O2	1.3350 (15)	C11—C12	1.523 (2)
C1—N2	1.3380 (19)	C11—H11A	0.9900
O2—C2	1.4467 (17)	C11—H11B	0.9900
C2—C3	1.5066 (18)	C12—H12A	0.9800
C2—H2A	0.9900	C12—H12B	0.9800
C2—H2B	0.9900	C12—H12C	0.9800
C3—C8	1.381 (2)	C13—C14	1.527 (2)
C3—C4	1.389 (2)	C13—H13A	0.9900
C4—C5	1.392 (2)	C13—H13B	0.9900
C4—H4	0.9500	C14—C15	1.530 (2)
C5—C6	1.375 (3)	C14—H14A	0.9900
C5—H5	0.9500	C14—H14B	0.9900
C6—C7	1.374 (2)	C15—H15A	0.9800
C6—H6	0.9500	C15—H15B	0.9800
C7—C8	1.396 (2)	C15—H15C	0.9800
C7—H7	0.9500	N3—C16	1.1582 (19)
C8—H8	0.9500	C16—S1	1.6386 (16)
N2—N1	1.3985 (15)
N3—Ni1—N3^i	180.00 (7)	N1—N2—H2N	122.8 (12)
N3—Ni1—O1^i	91.21 (4)	C9—N1—N2	116.57 (11)
N3^i—Ni1—O1^i	88.79 (4)	C9—N1—Ni1	136.26 (9)
N3—Ni1—O1	88.79 (4)	N2—N1—Ni1	106.86 (8)
N3^i—Ni1—O1	91.21 (4)	N1—C9—C13	118.34 (12)
O1^i—Ni1—O1	180.0	N1—C9—C10	124.70 (12)
N3—Ni1—N1^i	88.34 (5)	C13—C9—C10	116.88 (13)
N3^i—Ni1—N1^i	91.66 (5)	C9—C10—C11	110.23 (12)
O1^i—Ni1—N1^i	78.29 (4)	C9—C10—H10A	109.6
O1—Ni1—N1^i	101.71 (4)	C11—C10—H10A	109.6
N3—Ni1—N1	91.66 (5)	C9—C10—H10B	109.6
N3^i—Ni1—N1	88.34 (5)	C11—C10—H10B	109.6
O1^i—Ni1—N1	101.71 (4)	H10A—C10—H10B	108.1
O1—Ni1—N1	78.29 (4)	C12—C11—C10	112.14 (14)
N1^i—Ni1—N1	180.0	C12—C11—H11A	109.2
C1—O1—Ni1	110.38 (9)	C10—C11—H11A	109.2
O1—C1—O2	124.76 (13)	C12—C11—H11B	109.2
O1—C1—N2	124.70 (12)	C10—C11—H11B	109.2
O2—C1—N2	110.53 (12)	H11A—C11—H11B	107.9
C1—O2—C2	116.34 (11)	C11—C12—H12A	109.5
O2—C2—C3	107.88 (12)	C11—C12—H12B	109.5
O2—C2—H2A	110.1	H12A—C12—H12B	109.5
C3—C2—H2A	110.1	C11—C12—H12C	109.5
O2—C2—H2B	110.1	H12A—C12—H12C	109.5
C3—C2—H2B	110.1	H12B—C12—H12C	109.5
H2A—C2—H2B	108.4	C9—C13—C14	111.94 (12)
C8—C3—C4	119.14 (13)	C9—C13—H13A	109.2
C8—C3—C2	122.57 (13)	C14—C13—H13A	109.2
C4—C3—C2	118.26 (14)	C9—C13—H13B	109.2
C3—C4—C5	120.33 (17)	C14—C13—H13B	109.2
C3—C4—H4	119.8	H13A—C13—H13B	107.9
C5—C4—H4	119.8	C13—C14—C15	111.43 (15)
C6—C5—C4	120.24 (16)	C13—C14—H14A	109.3
C6—C5—H5	119.9	C15—C14—H14A	109.3
C4—C5—H5	119.9	C13—C14—H14B	109.3
C7—C6—C5	119.73 (14)	C15—C14—H14B	109.3
C7—C6—H6	120.1	H14A—C14—H14B	108.0
C5—C6—H6	120.1	C14—C15—H15A	109.5
C6—C7—C8	120.48 (16)	C14—C15—H15B	109.5
C6—C7—H7	119.8	H15A—C15—H15B	109.5
C8—C7—H7	119.8	C14—C15—H15C	109.5
C3—C8—C7	120.07 (15)	H15A—C15—H15C	109.5
C3—C8—H8	120.0	H15B—C15—H15C	109.5
C7—C8—H8	120.0	C16—N3—Ni1	163.23 (11)
C1—N2—N1	116.66 (11)	N3—C16—S1	178.75 (14)
C1—N2—H2N	120.5 (12)
Ni1—O1—C1—O2	169.27 (11)	O1—C1—N2—N1	−2.4 (2)
Ni1—O1—C1—N2	−11.39 (18)	O2—C1—N2—N1	177.07 (12)
O1—C1—O2—C2	6.7 (2)	C1—N2—N1—C9	−160.49 (13)
N2—C1—O2—C2	−172.72 (12)	C1—N2—N1—Ni1	14.19 (15)
C1—O2—C2—C3	168.23 (12)	N2—N1—C9—C13	179.49 (12)
O2—C2—C3—C8	−19.5 (2)	Ni1—N1—C9—C13	6.9 (2)
O2—C2—C3—C4	162.63 (15)	N2—N1—C9—C10	3.0 (2)
C8—C3—C4—C5	0.4 (3)	Ni1—N1—C9—C10	−169.67 (10)
C2—C3—C4—C5	178.27 (17)	N1—C9—C10—C11	79.24 (18)
C3—C4—C5—C6	0.2 (3)	C13—C9—C10—C11	−97.34 (15)
C4—C5—C6—C7	−0.3 (3)	C9—C10—C11—C12	173.28 (14)
C5—C6—C7—C8	−0.3 (3)	N1—C9—C13—C14	101.19 (16)
C4—C3—C8—C7	−0.9 (2)	C10—C9—C13—C14	−82.00 (17)
C2—C3—C8—C7	−178.70 (15)	C9—C13—C14—C15	173.33 (13)
C6—C7—C8—C3	0.8 (3)

Symmetry code: (i) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, º)

Cg is the centroid of the C3–C8 phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···S1^ii	0.824 (17)	2.507 (17)	3.2830 (12)	157.3 (16)
C8—H8···S1^ii	0.95	2.94	3.7080 (16)	139
C10—H10A···S1^ii	0.99	3.00	3.9059 (14)	154
C10—H10B···S1^iii	0.99	2.94	3.8464 (15)	153
C13—H13A···O1^i	0.99	2.35	3.1783 (18)	141
C2—H2A···Cg3^iv	0.99	2.72	3.6041 (17)	149

Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1, y−1/2, −z+5/2; (iii) x, y−1, z; (iv) −x, −y, −z+2.