Crystal structure of a new mixed-metal coordin­ation polymer consisting of Ni^II piperidine-di­thio­carbamate and penta­nuclear Cu^I—I cluster units

A novel heterometallic Cu^I–Ni^II coordination polymer with an infinite one-dimensional structure was prepared and structurally characterized via X-ray diffraction. This complex consists of a mononuclear nickel(II) unit of Ni^II(C₆H₁₀NS₂)₂ and a penta­nuclear copper(I) cluster unit of Cu₅I₅(CH₃CH₂CN).

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.021
• wR factor = 0.048
• Data-to-parameter ratio = 29.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.17 Report
PLAT431_ALERT_2_C Short Inter HL..A Contact Cl2      ..S1        .       3.44 Ang.
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          3 Report
PLAT971_ALERT_2_C Check Calcd Resid. Dens.  0.74A   From I4              2.43 eA-3

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          5 Note
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          1 Info
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT164_ALERT_4_G Nr. of Refined C-H H-Atoms in Heavy-Atom Struct.          3 Note
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          2 Report
PLAT173_ALERT_4_G The CIF-Embedded .res File Contains DANG Records          2 Report
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) I1       --Cu1       .       18.8 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) I1       --Cu2       .       22.5 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) I2       --Cu1       .       12.9 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) I2       --Cu2       .       30.5 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) I2       --Cu3       .       20.9 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) I3       --Cu1       .       39.2 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) I3       --Cu3       .       58.2 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) I4       --Cu3       .       10.3 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Cu3      --S2        .       16.0 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Ni1      --S1        .        5.3 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Ni1      --S2        .        6.3 s.u.
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          6 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        530 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          2 Info

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  16 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


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

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Computing details

Data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: CrystalStructure (Rigaku, 2017); software used to prepare material for publication: CrystalStructure (Rigaku, 2017).

Poly[[tetra-µ₃-iodido-µ₂-iodido-bis(µ₃-piperidine-1-dithiocarbamato)propionitrilepentacopper(I)nickel(II)] chloroform monosolvate]

Crystal data

[Cu5NiI5(C6H10NS2)2(C3H5N)]·CHCl3	F(000) = 1392
Mr = 1505.90	Dx = 2.770 Mg m^−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
a = 11.6906 (4) Å	Cell parameters from 10013 reflections
b = 13.2597 (3) Å	θ = 3.5–31.7°
c = 12.6351 (4) Å	µ = 8.15 mm^−1
β = 112.829 (4)°	T = 100 K
V = 1805.19 (11) Å^3	Block, black
Z = 2	0.10 × 0.05 × 0.02 mm

Data collection

Rigaku XtaLAB P200 diffractometer	5007 reflections with I > 2σ(I)
Detector resolution: 5.811 pixels mm^-1	Rint = 0.037
ω scans	θmax = 31.5°, θmin = 3.0°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015)	h = −16→15
Tmin = 0.547, Tmax = 0.850	k = −19→17
22696 measured reflections	l = −18→17
5667 independent reflections

Refinement

Refinement on F^2	6 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.021	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.048	w = 1/[σ^2(Fo^2) + (0.0175P)^2 + 1.401P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
5667 reflections	Δρmax = 2.37 e Å^−3
192 parameters	Δρmin = −1.09 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.

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

	x	y	z	Uiso*/Ueq
Cu1	0.07870 (3)	0.35696 (2)	0.22826 (3)	0.01492 (6)
Cu2	0.06118 (4)	0.250000	0.40244 (4)	0.01831 (9)
Cu3	−0.17631 (3)	0.36078 (2)	0.09941 (3)	0.01699 (6)
I1	0.27076 (2)	0.250000	0.36316 (2)	0.01584 (5)
I2	−0.07921 (2)	0.41447 (2)	0.31791 (2)	0.01423 (4)
I3	−0.01641 (2)	0.250000	0.03136 (2)	0.01220 (5)
I4	−0.37218 (2)	0.250000	0.04357 (2)	0.01957 (5)
C1	0.2475 (2)	0.49357 (15)	0.13153 (19)	0.0107 (4)
C2	0.4150 (2)	0.50565 (19)	0.32142 (19)	0.0160 (4)
H2A	0.452733	0.443559	0.364245	0.019*
H2B	0.346889	0.526878	0.344631	0.019*
C3	0.5122 (3)	0.5885 (2)	0.3494 (2)	0.0232 (5)
H3A	0.547669	0.600974	0.433227	0.028*
H3B	0.472716	0.651752	0.310579	0.028*
C4	0.6153 (2)	0.5587 (2)	0.3103 (2)	0.0261 (6)
H4A	0.675553	0.614794	0.325656	0.031*
H4B	0.659849	0.499170	0.354421	0.031*
C5	0.5627 (2)	0.5341 (2)	0.1827 (2)	0.0230 (5)
H5A	0.630165	0.508520	0.160911	0.028*
H5B	0.529464	0.596390	0.138249	0.028*
C6	0.4598 (2)	0.4552 (2)	0.1520 (2)	0.0180 (5)
H6A	0.420231	0.447714	0.067571	0.022*
H6B	0.495615	0.389276	0.185189	0.022*
C7	0.1007 (3)	0.250000	0.6602 (3)	0.0204 (7)
C8	0.1078 (4)	0.250000	0.7786 (3)	0.0293 (9)
H8	0.0609 (16)	0.18967 (4)	0.785 (3)	0.035*
C9	0.2415 (3)	0.250000	0.8654 (3)	0.0208 (7)
H9A	0.239 (2)	0.250000	0.9419 (10)	0.031*
H9B	0.2854 (9)	0.31033 (4)	0.8565 (13)	0.031*
C10	0.2395 (3)	0.750000	0.5209 (3)	0.0186 (7)
H10	0.199610	0.750000	0.578017	0.022*
N1	0.36544 (17)	0.48550 (15)	0.19678 (16)	0.0126 (4)
N2	0.0960 (3)	0.250000	0.5678 (3)	0.0208 (6)
S1	0.13029 (5)	0.51728 (4)	0.18070 (5)	0.01093 (10)
S2	−0.18105 (5)	0.52020 (4)	0.01647 (5)	0.01091 (10)
Cl1	0.40231 (9)	0.750000	0.59606 (10)	0.0355 (2)
Cl2	0.19291 (7)	0.64075 (6)	0.43626 (7)	0.03187 (16)
Ni1	0.000000	0.500000	0.000000	0.00975 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01456 (13)	0.01491 (13)	0.01762 (14)	0.00098 (11)	0.00879 (11)	0.00196 (11)
Cu2	0.0192 (2)	0.0224 (2)	0.01331 (18)	0.000	0.00625 (16)	0.000
Cu3	0.01664 (14)	0.01694 (13)	0.01690 (14)	−0.00328 (11)	0.00597 (11)	0.00057 (11)
I1	0.00947 (9)	0.01538 (9)	0.02001 (10)	0.000	0.00278 (7)	0.000
I2	0.01474 (7)	0.01642 (7)	0.01366 (7)	0.00173 (5)	0.00783 (5)	−0.00004 (5)
I3	0.01564 (10)	0.00914 (8)	0.01352 (9)	0.000	0.00751 (7)	0.000
I4	0.01104 (10)	0.01378 (9)	0.03178 (12)	0.000	0.00600 (9)	0.000
C1	0.0116 (10)	0.0087 (9)	0.0119 (9)	−0.0013 (7)	0.0046 (8)	0.0007 (7)
C2	0.0137 (10)	0.0211 (11)	0.0115 (10)	−0.0031 (9)	0.0030 (8)	−0.0021 (8)
C3	0.0184 (12)	0.0244 (13)	0.0228 (13)	−0.0074 (10)	0.0036 (10)	−0.0061 (10)
C4	0.0134 (11)	0.0374 (15)	0.0252 (13)	−0.0086 (11)	0.0049 (10)	0.0037 (12)
C5	0.0120 (11)	0.0350 (14)	0.0224 (12)	−0.0010 (10)	0.0073 (9)	0.0076 (11)
C6	0.0119 (10)	0.0259 (12)	0.0175 (11)	0.0024 (9)	0.0070 (8)	−0.0015 (9)
C7	0.0152 (15)	0.0261 (17)	0.0176 (16)	0.000	0.0038 (13)	0.000
C8	0.0218 (18)	0.050 (3)	0.0166 (17)	0.000	0.0082 (14)	0.000
C9	0.0230 (18)	0.0214 (16)	0.0178 (16)	0.000	0.0079 (14)	0.000
C10	0.0164 (16)	0.0209 (16)	0.0188 (16)	0.000	0.0070 (13)	0.000
N1	0.0090 (8)	0.0164 (9)	0.0125 (8)	−0.0003 (7)	0.0043 (7)	−0.0020 (7)
N2	0.0186 (14)	0.0245 (15)	0.0178 (14)	0.000	0.0054 (11)	0.000
S1	0.0094 (2)	0.0128 (2)	0.0110 (2)	−0.00043 (19)	0.00435 (18)	−0.00117 (18)
S2	0.0106 (2)	0.0120 (2)	0.0101 (2)	−0.00024 (19)	0.00394 (18)	−0.00100 (18)
Cl1	0.0190 (4)	0.0285 (5)	0.0436 (6)	0.000	−0.0048 (4)	0.000
Cl2	0.0251 (3)	0.0354 (4)	0.0314 (3)	0.0004 (3)	0.0068 (3)	−0.0173 (3)
Ni1	0.00797 (17)	0.01081 (17)	0.00993 (17)	−0.00041 (14)	0.00288 (14)	−0.00080 (14)

Geometric parameters (Å, º)

Cu1—S1	2.3505 (6)	C4—H4A	0.9900
Cu1—I2	2.6259 (3)	C4—H4B	0.9900
Cu1—I1	2.6435 (4)	C5—C6	1.526 (4)
Cu1—I3	2.7001 (4)	C5—H5A	0.9900
Cu2—N2	1.968 (3)	C5—H5B	0.9900
Cu2—I1	2.6820 (5)	C6—N1	1.476 (3)
Cu2—I2	2.6889 (3)	C6—H6A	0.9900
Cu2—I2^i	2.6889 (3)	C6—H6B	0.9900
Cu3—S2	2.3505 (6)	C7—N2	1.147 (5)
Cu3—I4	2.5778 (4)	C7—C8	1.466 (5)
Cu3—I2	2.6429 (4)	C8—C9	1.521 (5)
Cu3—I3	2.7637 (4)	C8—H8	0.9901 (10)
C1—N1	1.307 (3)	C8—H8^i	0.9901 (10)
C1—S2^ii	1.734 (2)	C9—H9A	0.9800 (10)
C1—S1	1.739 (2)	C9—H9B	0.9800 (10)
C2—N1	1.476 (3)	C9—H9B^i	0.9800 (10)
C2—C3	1.521 (3)	C10—Cl2	1.757 (2)
C2—H2A	0.9900	C10—Cl2^iii	1.757 (2)
C2—H2B	0.9900	C10—Cl1	1.767 (4)
C3—C4	1.523 (4)	C10—H10	1.0000
C3—H3A	0.9900	S1—Ni1	2.2106 (5)
C3—H3B	0.9900	S2—Ni1	2.2219 (5)
C4—C5	1.521 (4)
Cu1···Cu2	2.6920 (5)	Cu1···Cu1^i	2.8366 (6)
Cu1···Cu3	2.7883 (4)	Cu3···Cu3^i	2.9378 (6)
S1—Cu1—I2	98.089 (17)	S2^ii—C1—S1	108.58 (12)
S1—Cu1—I1	114.335 (17)	N1—C2—C3	109.1 (2)
I2—Cu1—I1	116.170 (13)	N1—C2—H2A	109.9
S1—Cu1—Cu2	142.553 (19)	C3—C2—H2A	109.9
I2—Cu1—Cu2	60.730 (11)	N1—C2—H2B	109.9
I1—Cu1—Cu2	60.344 (12)	C3—C2—H2B	109.9
S1—Cu1—I3	107.115 (17)	H2A—C2—H2B	108.3
I2—Cu1—I3	116.286 (12)	C2—C3—C4	110.6 (2)
I1—Cu1—I3	104.798 (11)	C2—C3—H3A	109.5
Cu2—Cu1—I3	109.985 (12)	C4—C3—H3A	109.5
S1—Cu1—Cu3	99.008 (17)	C2—C3—H3B	109.5
I2—Cu1—Cu3	58.346 (10)	C4—C3—H3B	109.5
I1—Cu1—Cu3	146.557 (14)	H3A—C3—H3B	108.1
Cu2—Cu1—Cu3	94.797 (15)	C5—C4—C3	110.8 (2)
I3—Cu1—Cu3	60.446 (10)	C5—C4—H4A	109.5
S1—Cu1—Cu1^i	154.742 (15)	C3—C4—H4A	109.5
I2—Cu1—Cu1^i	106.881 (7)	C5—C4—H4B	109.5
I1—Cu1—Cu1^i	57.554 (7)	C3—C4—H4B	109.5
Cu2—Cu1—Cu1^i	58.208 (8)	H4A—C4—H4B	108.1
I3—Cu1—Cu1^i	58.314 (7)	C4—C5—C6	111.8 (2)
Cu3—Cu1—Cu1^i	91.040 (8)	C4—C5—H5A	109.3
N2—Cu2—I1	111.67 (9)	C6—C5—H5A	109.3
N2—Cu2—I2	105.34 (5)	C4—C5—H5B	109.3
I1—Cu2—I2	112.776 (11)	C6—C5—H5B	109.3
N2—Cu2—I2^i	105.34 (5)	H5A—C5—H5B	107.9
I1—Cu2—I2^i	112.776 (12)	N1—C6—C5	110.5 (2)
I2—Cu2—I2^i	108.395 (17)	N1—C6—H6A	109.6
N2—Cu2—Cu1	144.91 (4)	C5—C6—H6A	109.6
I1—Cu2—Cu1	58.933 (12)	N1—C6—H6B	109.6
I2—Cu2—Cu1	58.418 (9)	C5—C6—H6B	109.6
I2^i—Cu2—Cu1	109.322 (16)	H6A—C6—H6B	108.1
N2—Cu2—Cu1^i	144.90 (4)	N2—C7—C8	179.5 (4)
I1—Cu2—Cu1^i	58.932 (12)	C7—C8—C9	111.8 (3)
I2—Cu2—Cu1^i	109.322 (16)	C7—C8—H8	105.5 (19)
I2^i—Cu2—Cu1^i	58.419 (9)	C9—C8—H8	112.9 (16)
Cu1—Cu2—Cu1^i	63.585 (16)	C7—C8—H8^i	105.5 (19)
S2—Cu3—I4	121.711 (19)	C9—C8—H8^i	112.9 (17)
S2—Cu3—I2	98.612 (17)	H8—C8—H8^i	107.80 (19)
I4—Cu3—I2	114.539 (14)	C8—C9—H9A	107.0 (15)
S2—Cu3—I3	103.950 (17)	C8—C9—H9B	110.8 (8)
I4—Cu3—I3	104.370 (12)	H9A—C9—H9B	109.44 (16)
I2—Cu3—I3	113.573 (12)	C8—C9—H9B^i	110.8 (8)
S2—Cu3—Cu1	96.405 (18)	H9A—C9—H9B^i	109.44 (16)
I4—Cu3—Cu1	141.671 (14)	H9B—C9—H9B^i	109.4 (2)
I2—Cu3—Cu1	57.751 (10)	Cl2—C10—Cl2^iii	111.1 (2)
I3—Cu3—Cu1	58.198 (10)	Cl2—C10—Cl1	110.00 (14)
S2—Cu3—Cu3^i	154.073 (15)	Cl2^iii—C10—Cl1	110.00 (14)
I4—Cu3—Cu3^i	55.263 (8)	Cl2—C10—H10	108.6
I2—Cu3—Cu3^i	105.626 (7)	Cl2^iii—C10—H10	108.6
I3—Cu3—Cu3^i	57.894 (7)	Cl1—C10—H10	108.6
Cu1—Cu3—Cu3^i	88.961 (8)	C1—N1—C2	122.64 (19)
Cu1—I1—Cu1^i	64.893 (14)	C1—N1—C6	122.8 (2)
Cu1—I1—Cu2	60.724 (11)	C2—N1—C6	114.55 (18)
Cu1^i—I1—Cu2	60.724 (11)	C7—N2—Cu2	171.6 (3)
Cu1—I2—Cu3	63.902 (10)	C1—S1—Ni1	86.27 (7)
Cu1—I2—Cu2	60.851 (12)	C1—S1—Cu1	104.11 (7)
Cu3—I2—Cu2	98.341 (12)	Ni1—S1—Cu1	91.60 (2)
Cu1—I3—Cu1^i	63.372 (13)	C1^ii—S2—Ni1	86.04 (8)
Cu1—I3—Cu3	61.356 (10)	C1^ii—S2—Cu3	108.01 (7)
Cu1^i—I3—Cu3	94.530 (11)	Ni1—S2—Cu3	94.29 (2)
Cu1—I3—Cu3^i	94.530 (11)	S1—Ni1—S1^ii	180.0
Cu1^i—I3—Cu3^i	61.357 (10)	S1—Ni1—S2^ii	79.02 (2)
Cu3—I3—Cu3^i	64.211 (13)	S1^ii—Ni1—S2^ii	100.98 (2)
Cu3—I4—Cu3^i	69.475 (15)	S1—Ni1—S2	100.98 (2)
N1—C1—S2^ii	126.40 (18)	S1^ii—Ni1—S2	79.02 (2)
N1—C1—S1	125.01 (17)	S2^ii—Ni1—S2	180.0
N1—C2—C3—C4	−57.4 (3)	C3—C2—N1—C1	−121.9 (2)
C2—C3—C4—C5	56.4 (3)	C3—C2—N1—C6	58.3 (3)
C3—C4—C5—C6	−53.4 (3)	C5—C6—N1—C1	124.8 (2)
C4—C5—C6—N1	51.7 (3)	C5—C6—N1—C2	−55.4 (3)
S2^ii—C1—N1—C2	175.50 (17)	N1—C1—S1—Ni1	−176.18 (19)
S1—C1—N1—C2	−6.1 (3)	S2^ii—C1—S1—Ni1	2.44 (9)
S2^ii—C1—N1—C6	−4.7 (3)	N1—C1—S1—Cu1	−85.46 (19)
S1—C1—N1—C6	173.69 (18)	S2^ii—C1—S1—Cu1	93.16 (10)

Symmetry codes: (i) x, −y+1/2, z; (ii) −x, −y+1, −z; (iii) x, −y+3/2, z.