Crystal structure and characterization of a new copper(II) chloride dimer with meth­yl(pyridin-2-yl­methyl­idene)amine

The new copper(II) complex [CuLCl₂]₂, where L is a product of Schiff base condensation between methyl­amine and 2-pyridine­carbaldehyde, is built of discrete centrosymmetric dimers.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.021
• wR factor = 0.054
• Data-to-parameter ratio = 38.2

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Theta(Min).          7 Note
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          2 Report

Alert level G
PLAT019_ALERT_1_G _diffrn_measured_fraction_theta_full/*_max < 1.0      0.997 Report
PLAT154_ALERT_1_G The s.u.'s on the Cell Angles are Equal ..(Note)      0.005 Degree
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu1      --N1       .        7.0 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu1      --N22      .        5.5 s.u.
PLAT794_ALERT_5_G Tentative Bond Valency for Cu1       (II)      .       2.10 Info
PLAT802_ALERT_4_G CIF Input Record(s) with more than 80 Characters          1 Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          3 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
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......     Please Check
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          5 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
   4 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
   2 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, 2016); cell refinement: CrysAlis PRO (Rigaku OD, 2016); data reduction: CrysAlis PRO (Rigaku OD, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 1999), Mercury (Macrae, 2020); software used to prepare material for publication: WinGX (Farrugia, 2012).

Di-µ-chlorido-bis{chlorido[methyl(pyridin-2-ylmethylidene)amine-κ²N,N']copper(II)}

Crystal data

[Cu2Cl4(C7H8N2)2]	Z = 1
Mr = 509.19	F(000) = 254
Triclinic, P1	Dx = 1.884 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7054 (5) Å	Cell parameters from 7922 reflections
b = 7.7240 (5) Å	θ = 4.0–37.5°
c = 8.5606 (5) Å	µ = 2.97 mm^−1
α = 103.659 (5)°	T = 100 K
β = 98.803 (5)°	Plate, green
γ = 110.273 (5)°	0.56 × 0.41 × 0.16 mm
V = 448.74 (5) Å^3

Data collection

Oxford Diffraction Gemini diffractometer	4238 independent reflections
Graphite monochromator	3866 reflections with I > 2σ(I)
Detector resolution: 10.4738 pixels mm^-1	Rint = 0.024
ω scans	θmax = 36.0°, θmin = 4.2°
Absorption correction: analytical (CrysAlis Pro; Rigaku OD, 2016)	h = −12→12
Tmin = 0.367, Tmax = 0.669	k = −12→12
13153 measured reflections	l = −14→14

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.021	w = 1/[σ^2(Fo^2) + (0.0232P)^2 + 0.1399P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.054	(Δ/σ)max = 0.002
S = 1.08	Δρmax = 0.68 e Å^−3
4238 reflections	Δρmin = −0.52 e Å^−3
111 parameters	Extinction correction: SHELXL-2017/1 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.018 (2)

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 low theta reflection was omitted from the refinement.

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

	x	y	z	Uiso*/Ueq
Cu1	0.50923 (2)	0.72999 (2)	0.57914 (2)	0.01020 (4)
Cl1	0.73459 (3)	0.54548 (3)	0.59992 (3)	0.01344 (5)
Cl2	0.36774 (3)	0.72631 (3)	0.79030 (3)	0.01500 (5)
N1	0.73406 (12)	0.98020 (12)	0.71584 (10)	0.01113 (13)
C2	0.82713 (14)	1.08198 (14)	0.62321 (12)	0.01197 (15)
C21	0.74454 (15)	0.99108 (15)	0.44328 (12)	0.01362 (16)
H21	0.797176	1.050864	0.36667	0.016*
N22	0.59926 (13)	0.82859 (13)	0.39284 (10)	0.01293 (14)
C23	0.51841 (17)	0.72996 (17)	0.21469 (12)	0.01786 (18)
H23A	0.580724	0.81486	0.153155	0.027*
H23B	0.380672	0.699047	0.18678	0.027*
H23C	0.539512	0.609696	0.184401	0.027*
C3	0.98700 (15)	1.25492 (15)	0.69291 (13)	0.01513 (17)
H3	1.047781	1.324625	0.625083	0.018*
C4	1.05621 (15)	1.32381 (15)	0.86576 (14)	0.01670 (18)
H4	1.166445	1.441282	0.917816	0.02*
C5	0.96252 (15)	1.21913 (15)	0.96081 (13)	0.01547 (17)
H5	1.008301	1.263236	1.078576	0.019*
C6	0.79997 (14)	1.04805 (14)	0.88085 (12)	0.01344 (16)
H6	0.734271	0.977774	0.946118	0.016*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01109 (6)	0.00923 (6)	0.00822 (5)	0.00253 (4)	0.00183 (4)	0.00182 (4)
Cl1	0.01209 (9)	0.01174 (9)	0.01270 (9)	0.00393 (7)	−0.00076 (7)	0.00086 (7)
Cl2	0.01607 (10)	0.01358 (10)	0.01276 (9)	0.00224 (8)	0.00631 (8)	0.00342 (7)
N1	0.0127 (3)	0.0098 (3)	0.0105 (3)	0.0037 (3)	0.0030 (3)	0.0034 (2)
C2	0.0132 (4)	0.0110 (4)	0.0128 (4)	0.0046 (3)	0.0050 (3)	0.0049 (3)
C21	0.0170 (4)	0.0150 (4)	0.0125 (4)	0.0082 (3)	0.0061 (3)	0.0065 (3)
N22	0.0162 (4)	0.0142 (4)	0.0094 (3)	0.0075 (3)	0.0029 (3)	0.0037 (3)
C23	0.0238 (5)	0.0209 (5)	0.0087 (4)	0.0100 (4)	0.0027 (3)	0.0037 (3)
C3	0.0143 (4)	0.0118 (4)	0.0188 (4)	0.0034 (3)	0.0063 (3)	0.0052 (3)
C4	0.0136 (4)	0.0119 (4)	0.0200 (4)	0.0021 (3)	0.0033 (3)	0.0020 (3)
C5	0.0149 (4)	0.0130 (4)	0.0135 (4)	0.0032 (3)	0.0008 (3)	0.0009 (3)
C6	0.0148 (4)	0.0120 (4)	0.0102 (3)	0.0029 (3)	0.0015 (3)	0.0024 (3)

Geometric parameters (Å, º)

Cu1—N1	2.0241 (9)	N22—C23	1.4580 (13)
Cu1—N22	2.0374 (8)	C23—H23A	0.98
Cu1—Cl2	2.2500 (3)	C23—H23B	0.98
Cu1—Cl1^i	2.2835 (3)	C23—H23C	0.98
Cu1—Cl1	2.6112 (3)	C3—C4	1.3953 (15)
N1—C6	1.3320 (12)	C3—H3	0.95
N1—C2	1.3561 (12)	C4—C5	1.3867 (15)
C2—C3	1.3842 (14)	C4—H4	0.95
C2—C21	1.4663 (14)	C5—C6	1.3953 (14)
C21—N22	1.2796 (13)	C5—H5	0.95
C21—H21	0.95	C6—H6	0.95
N1—Cu1—N22	80.20 (3)	C21—N22—Cu1	114.21 (7)
N1—Cu1—Cl2	92.29 (2)	C23—N22—Cu1	126.45 (7)
N22—Cu1—Cl2	155.16 (3)	N22—C23—H23A	109.5
N1—Cu1—Cl1^i	173.79 (2)	N22—C23—H23B	109.5
N22—Cu1—Cl1^i	93.61 (3)	H23A—C23—H23B	109.5
Cl2—Cu1—Cl1^i	93.600 (11)	N22—C23—H23C	109.5
N1—Cu1—Cl1	88.81 (3)	H23A—C23—H23C	109.5
N22—Cu1—Cl1	94.79 (3)	H23B—C23—H23C	109.5
Cl2—Cu1—Cl1	108.803 (10)	C2—C3—C4	118.02 (9)
Cl1^i—Cu1—Cl1	91.137 (10)	C2—C3—H3	121
Cu1^i—Cl1—Cu1	88.864 (11)	C4—C3—H3	121
C6—N1—C2	118.79 (8)	C5—C4—C3	119.36 (9)
C6—N1—Cu1	127.36 (7)	C5—C4—H4	120.3
C2—N1—Cu1	113.81 (6)	C3—C4—H4	120.3
N1—C2—C3	122.78 (9)	C4—C5—C6	118.99 (10)
N1—C2—C21	113.95 (8)	C4—C5—H5	120.5
C3—C2—C21	123.26 (9)	C6—C5—H5	120.5
N22—C21—C2	117.82 (8)	N1—C6—C5	122.05 (9)
N22—C21—H21	121.1	N1—C6—H6	119
C2—C21—H21	121.1	C5—C6—H6	119
C21—N22—C23	119.31 (9)
C6—N1—C2—C3	−0.69 (15)	N1—C2—C3—C4	1.35 (16)
Cu1—N1—C2—C3	−178.63 (8)	C21—C2—C3—C4	−177.87 (10)
C6—N1—C2—C21	178.59 (9)	C2—C3—C4—C5	−0.67 (16)
Cu1—N1—C2—C21	0.66 (11)	C3—C4—C5—C6	−0.57 (17)
N1—C2—C21—N22	−0.97 (14)	C2—N1—C6—C5	−0.66 (15)
C3—C2—C21—N22	178.31 (10)	Cu1—N1—C6—C5	176.97 (8)
C2—C21—N22—C23	−177.41 (9)	C4—C5—C6—N1	1.29 (17)
C2—C21—N22—Cu1	0.77 (12)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···Cl2	0.95	2.71	3.2301 (10)	115