Bis­[(S)-N-(2-butyl)-3,5-di­chlorosalicyl­idene­aminato-κ²N,O]copper(II)

The title compound, [Cu(C₁₁H₁₂Cl₂NO)₂], has a compressed tetrahedral trans-[CuN₂O₂] coordination environment. The absolute configuration is found to be Δ(S,S) for the crystal examined. The Cu—N bond distances are 1.969 (4) and 1.971 (4) Å, while the Cu—O bond distances are 1.886 (3) and 1.892 (3) Å. The ligands, containing optically active (S)-2-butyl­amine moieties and electron-withdrawing Cl substituents, lead to an umbrella conformation of the overall mol­ecule. On heating to 387 K, a structural phase transition is observed, probably involving a change in coordination geometry.

Key indicators

• Single-crystal X-ray study
• T = 297 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.047
• wR factor = 0.107
• Data-to-parameter ratio = 9.8

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT052_ALERT_1_A (Proper) Absorption Correction Method Missing ..          ?

Alert level C
REFNR01_ALERT_3_C  Ratio of reflections to parameters is < 10 for a
            non-centrosymmetric structure, where ZMAX > 18
            sine(theta)/lambda                0.6495
            Proportion of unique data used    0.8382
            Ratio reflections to parameters   9.8114
PLAT057_ALERT_3_C Correction for Absorption Required   RT(exp) ...       1.13
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.98 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C15    -   C16     ..       5.62 su
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors  for        C16
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors  for        C19
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          8
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C22 H24 Cl4 Cu N2 O2

Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           27.49
           From the CIF: _reflns_number_total               3289
           Count of symmetry unique reflns         3289
           Completeness (_total/calc)            100.00%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present          yes

   1 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   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

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Computing details

Data collection: WinAFC Diffractometer Control Software (Rigaku, 1999); cell refinement: WinAFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 2001); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.

(I)

Crystal data

[Cu(C11H12Cl2NO)2]	F(000) = 1132.0
Mr = 553.78	Dx = 1.443 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 13.825 (3) Å	θ = 10.1–12.5°
b = 17.563 (5) Å	µ = 1.30 mm^−1
c = 10.499 (1) Å	T = 297 K
V = 2549.3 (9) Å^3	Prismatic, brown
Z = 4	0.40 × 0.40 × 0.30 mm

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.019
ω/2θ scans	θmax = 27.5°
Absorption correction: ψ scan (North et al., 1968)	h = −7→17
Tmin = 0.601, Tmax = 0.678	k = −22→9
4081 measured reflections	l = −5→13
3289 independent reflections	3 standard reflections every 150 reflections
2757 reflections with I > 2σ(I)	intensity decay: 1.2%

Refinement

Refinement on F^2	w = 1/[σ^2(Fo^2) + (0.0462P)^2 + 1.0606P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.047	(Δ/σ)max = 0.001
wR(F^2) = 0.107	Δρmax = 0.41 e Å^−3
S = 1.02	Δρmin = −0.54 e Å^−3
2757 reflections	Absolute structure: Flack (1983), with xx Friedel pairs
281 parameters	Absolute structure parameter: −0.01 (2)
H-atom parameters constrained

Special details

Refinement. Refinement using reflections with F² > 0.0 σ(F²). The weighted R-factor (wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq
Cu1	−0.95539 (4)	−0.14096 (3)	−0.79637 (5)	0.0526 (2)
Cl1	−0.9235 (1)	0.11347 (7)	−0.9368 (1)	0.0730 (3)
Cl2	−0.6843 (1)	0.17963 (9)	−0.5513 (2)	0.1006 (6)
Cl3	−0.8654 (1)	−0.39945 (8)	−0.8017 (2)	0.0937 (5)
Cl4	−1.0889 (2)	−0.4519 (2)	−1.2100 (2)	0.1471 (9)
O1	−0.9284 (2)	−0.0371 (2)	−0.8247 (3)	0.0614 (8)
O2	−0.9452 (3)	−0.2479 (2)	−0.8130 (3)	0.0653 (8)
N1	−0.8868 (3)	−0.1419 (2)	−0.6321 (4)	0.0599 (9)
N2	−1.0651 (3)	−0.1365 (2)	−0.9161 (4)	0.0588 (9)
C1	−0.8239 (3)	−0.0124 (2)	−0.6467 (4)	0.0530 (9)
C2	−0.8739 (3)	0.0087 (2)	−0.7604 (4)	0.0518 (9)
C3	−0.8623 (3)	0.0844 (2)	−0.7999 (5)	0.0540 (9)
C4	−0.8064 (3)	0.1361 (3)	−0.7385 (5)	0.061 (1)
C5	−0.7563 (3)	0.1134 (3)	−0.6292 (5)	0.066 (1)
C6	−0.7642 (3)	0.0405 (3)	−0.5853 (5)	0.064 (1)
C7	−0.8357 (3)	−0.0862 (3)	−0.5903 (5)	0.061 (1)
C8	−0.8907 (5)	−0.2133 (3)	−0.5527 (6)	0.079 (2)
C9	−0.9255 (7)	−0.1981 (5)	−0.4191 (7)	0.109 (2)
C10	−0.7923 (6)	−0.2519 (4)	−0.5558 (8)	0.111 (3)
C11	−1.0263 (8)	−0.1686 (6)	−0.4119 (9)	0.154 (4)
C12	−1.0462 (4)	−0.2664 (3)	−0.9959 (5)	0.065 (1)
C13	−0.9778 (3)	−0.2900 (2)	−0.9051 (5)	0.059 (1)
C14	−0.9469 (4)	−0.3665 (3)	−0.9136 (5)	0.068 (1)
C15	−0.9799 (5)	−0.4150 (3)	−1.0068 (7)	0.092 (2)
C16	−1.0465 (6)	−0.3892 (4)	−1.0970 (6)	0.093 (2)
C17	−1.0781 (4)	−0.3161 (4)	−1.0905 (6)	0.087 (2)
C18	−1.0886 (3)	−0.1909 (3)	−0.9910 (5)	0.065 (1)
C19	−1.1223 (4)	−0.0649 (3)	−0.9216 (6)	0.072 (1)
C20	−1.2260 (5)	−0.0795 (4)	−0.8841 (8)	0.099 (2)
C21	−1.1128 (6)	−0.0275 (4)	−1.0513 (8)	0.112 (3)
C22	−1.2379 (6)	−0.1136 (5)	−0.7549 (10)	0.128 (3)
H1	−0.8013	0.1868	−0.7693	0.0730*
H2	−0.7285	0.0255	−0.5120	0.0769*
H3	−0.8016	−0.0950	−0.5130	0.0729*
H4	−0.9359	−0.2469	−0.5917	0.0950*
H5	−0.9223	−0.2446	−0.3726	0.1299*
H6	−0.8833	−0.1619	−0.3813	0.1299*
H7	−0.7950	−0.2984	−0.5096	0.1329*
H8	−0.7741	−0.2618	−0.6413	0.1329*
H9	−0.7454	−0.2193	−0.5174	0.1329*
H10	−1.0429	−0.1598	−0.3253	0.1863*
H11	−1.0305	−0.1221	−0.4580	0.1863*
H12	−1.0693	−0.2048	−0.4477	0.1863*
H13	−0.9574	−0.4660	−1.0099	0.1105*
H14	−1.1231	−0.2982	−1.1525	0.1043*
H15	−1.1395	−0.1807	−1.0495	0.0775*
H16	−1.0955	−0.0308	−0.8605	0.0874*
H17	−1.2599	−0.0323	−0.8856	0.1193*
H18	−1.2538	−0.1132	−0.9445	0.1193*
H19	−1.0468	−0.0181	−1.0692	0.1330*
H20	−1.1393	−0.0602	−1.1144	0.1330*
H21	−1.1475	0.0194	−1.0512	0.1330*
H22	−1.3046	−0.1221	−0.7383	0.1543*
H23	−1.2041	−0.1607	−0.7511	0.1543*
H24	−1.2124	−0.0799	−0.6926	0.1543*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0545 (3)	0.0472 (2)	0.0561 (3)	−0.0063 (2)	−0.0083 (2)	0.0023 (2)
Cl1	0.0816 (8)	0.0594 (6)	0.0781 (8)	−0.0041 (6)	−0.0106 (7)	0.0139 (6)
Cl2	0.097 (1)	0.0745 (8)	0.131 (1)	−0.0266 (8)	−0.037 (1)	−0.0161 (9)
Cl3	0.116 (1)	0.0673 (7)	0.098 (1)	0.0207 (8)	0.018 (1)	0.0058 (8)
Cl4	0.166 (2)	0.141 (2)	0.134 (2)	−0.037 (2)	0.008 (2)	−0.084 (2)
O1	0.069 (2)	0.051 (2)	0.064 (2)	−0.010 (1)	−0.016 (2)	0.003 (1)
O2	0.079 (2)	0.052 (2)	0.065 (2)	−0.010 (2)	−0.007 (2)	0.002 (1)
N1	0.064 (2)	0.055 (2)	0.061 (2)	−0.009 (2)	−0.012 (2)	0.008 (2)
N2	0.057 (2)	0.055 (2)	0.064 (2)	−0.008 (2)	−0.010 (2)	0.002 (2)
C1	0.045 (2)	0.052 (2)	0.062 (2)	−0.002 (2)	−0.004 (2)	−0.002 (2)
C2	0.048 (2)	0.049 (2)	0.058 (2)	−0.004 (2)	0.005 (2)	−0.003 (2)
C3	0.051 (2)	0.051 (2)	0.060 (2)	0.000 (2)	0.005 (2)	−0.003 (2)
C4	0.055 (2)	0.053 (2)	0.074 (3)	−0.007 (2)	0.013 (2)	−0.006 (2)
C5	0.058 (3)	0.061 (3)	0.079 (3)	−0.013 (2)	−0.003 (2)	−0.017 (3)
C6	0.060 (3)	0.064 (3)	0.068 (3)	−0.004 (2)	−0.011 (2)	−0.003 (2)
C7	0.063 (3)	0.058 (2)	0.061 (3)	−0.006 (2)	−0.015 (2)	0.005 (2)
C8	0.103 (4)	0.063 (3)	0.071 (3)	−0.015 (3)	−0.027 (3)	0.021 (3)
C9	0.140 (6)	0.109 (5)	0.078 (4)	−0.041 (5)	−0.013 (4)	0.024 (4)
C10	0.119 (5)	0.071 (3)	0.143 (7)	0.009 (4)	−0.043 (5)	0.026 (5)
C11	0.177 (9)	0.142 (8)	0.142 (8)	−0.034 (7)	0.053 (8)	0.017 (7)
C12	0.063 (3)	0.069 (3)	0.062 (3)	−0.019 (2)	0.002 (3)	−0.014 (2)
C13	0.064 (3)	0.050 (2)	0.064 (3)	−0.017 (2)	0.019 (2)	−0.004 (2)
C14	0.070 (3)	0.058 (2)	0.075 (3)	−0.007 (2)	0.027 (3)	−0.005 (2)
C15	0.099 (4)	0.068 (3)	0.109 (5)	−0.022 (3)	0.052 (4)	−0.031 (3)
C16	0.097 (4)	0.095 (4)	0.086 (4)	−0.032 (4)	0.020 (4)	−0.033 (4)
C17	0.084 (4)	0.091 (4)	0.085 (4)	−0.027 (3)	0.007 (3)	−0.025 (3)
C18	0.059 (3)	0.074 (3)	0.061 (3)	−0.015 (2)	−0.011 (2)	−0.001 (2)
C19	0.063 (3)	0.065 (3)	0.089 (4)	0.002 (2)	−0.020 (3)	0.007 (3)
C20	0.074 (4)	0.093 (4)	0.131 (6)	0.006 (3)	−0.012 (4)	0.007 (5)
C21	0.117 (5)	0.093 (4)	0.125 (6)	−0.006 (4)	−0.028 (5)	0.045 (5)
C22	0.127 (6)	0.113 (6)	0.145 (7)	0.009 (5)	0.048 (6)	−0.018 (6)

Geometric parameters (Å, º)

Cu1—O1	1.886 (3)	C9—H6	0.950
Cu1—O2	1.892 (3)	C10—H7	0.950
Cu1—N1	1.969 (4)	C10—H8	0.950
Cu1—N2	1.971 (4)	C10—H9	0.950
Cl1—C3	1.744 (5)	C11—H10	0.950
Cl2—C5	1.735 (5)	C11—H11	0.950
Cl3—C14	1.727 (5)	C11—H12	0.950
Cl4—C16	1.722 (7)	C12—C17	1.394 (8)
O1—C2	1.292 (5)	C12—C18	1.452 (7)
O2—C13	1.298 (6)	C13—C14	1.413 (7)
N1—C7	1.284 (6)	C14—C15	1.375 (8)
N1—C8	1.506 (7)	C15—C16	1.40 (1)
N2—C18	1.279 (6)	C15—H13	0.950
N2—C19	1.488 (6)	C16—C17	1.357 (10)
C1—C2	1.428 (6)	C17—H14	0.950
C1—C6	1.400 (7)	C18—H15	0.950
C1—C7	1.435 (6)	C19—C20	1.509 (9)
C2—C3	1.402 (6)	C19—C21	1.52 (1)
C3—C4	1.357 (6)	C19—H16	0.950
C4—C5	1.398 (7)	C20—C22	1.49 (1)
C4—H1	0.950	C20—H17	0.950
C5—C6	1.366 (7)	C20—H18	0.950
C6—H2	0.950	C21—H19	0.950
C7—H3	0.950	C21—H20	0.950
C8—C9	1.507 (9)	C21—H21	0.950
C8—C10	1.521 (10)	C22—H22	0.950
C8—H4	0.950	C22—H23	0.950
C9—C11	1.49 (1)	C22—H24	0.950
C9—H5	0.950
O1—Cu1—O2	158.7 (1)	H8—C10—H9	109.3
O1—Cu1—N1	92.9 (2)	C9—C11—H10	109.4
O1—Cu1—N2	90.8 (2)	C9—C11—H11	109.3
O2—Cu1—N1	92.1 (2)	C9—C11—H12	109.5
O2—Cu1—N2	92.2 (2)	H10—C11—H11	109.4
N1—Cu1—N2	158.4 (2)	H10—C11—H12	109.7
Cu1—O1—C2	129.4 (3)	H11—C11—H12	109.6
Cu1—O2—C13	127.5 (3)	C13—C12—C17	120.8 (5)
Cu1—N1—C7	123.9 (3)	C13—C12—C18	121.1 (4)
Cu1—N1—C8	118.3 (3)	C17—C12—C18	118.0 (5)
C7—N1—C8	117.7 (4)	O2—C13—C12	124.8 (4)
Cu1—N2—C18	124.0 (3)	O2—C13—C14	119.0 (4)
Cu1—N2—C19	117.8 (3)	C12—C13—C14	116.1 (4)
C18—N2—C19	118.2 (4)	Cl3—C14—C13	118.2 (4)
C2—C1—C6	119.9 (4)	Cl3—C14—C15	119.6 (4)
C2—C1—C7	121.6 (4)	C13—C14—C15	122.3 (5)
C6—C1—C7	118.5 (4)	C14—C15—C16	120.0 (6)
O1—C2—C1	123.9 (4)	C14—C15—H13	120.0
O1—C2—C3	120.1 (4)	C16—C15—H13	120.0
C1—C2—C3	116.0 (4)	Cl4—C16—C15	118.9 (5)
Cl1—C3—C2	117.8 (3)	Cl4—C16—C17	122.0 (5)
Cl1—C3—C4	118.2 (3)	C15—C16—C17	119.0 (6)
C2—C3—C4	124.0 (4)	C12—C17—C16	121.7 (6)
C3—C4—C5	118.8 (4)	C12—C17—H14	119.1
C3—C4—H1	120.5	C16—C17—H14	119.2
C5—C4—H1	120.7	N2—C18—C12	126.9 (4)
Cl2—C5—C4	118.7 (4)	N2—C18—H15	116.4
Cl2—C5—C6	121.0 (4)	C12—C18—H15	116.6
C4—C5—C6	120.3 (5)	N2—C19—C20	110.6 (4)
C1—C6—C5	120.9 (5)	N2—C19—C21	110.8 (5)
C1—C6—H2	119.6	N2—C19—H16	107.4
C5—C6—H2	119.5	C20—C19—C21	112.9 (6)
N1—C7—C1	127.6 (4)	C20—C19—H16	107.6
N1—C7—H3	116.2	C21—C19—H16	107.4
C1—C7—H3	116.2	C19—C20—C22	114.2 (6)
N1—C8—C9	112.3 (5)	C19—C20—H17	108.4
N1—C8—C10	109.1 (5)	C19—C20—H18	108.5
N1—C8—H4	107.6	C22—C20—H17	108.1
C9—C8—C10	112.6 (6)	C22—C20—H18	108.2
C9—C8—H4	107.5	H17—C20—H18	109.4
C10—C8—H4	107.6	C19—C21—H19	109.6
C8—C9—C11	114.1 (7)	C19—C21—H20	109.3
C8—C9—H5	108.1	C19—C21—H21	109.2
C8—C9—H6	108.1	H19—C21—H20	109.8
C11—C9—H5	108.5	H19—C21—H21	109.5
C11—C9—H6	108.7	H20—C21—H21	109.3
H5—C9—H6	109.3	C20—C22—H22	109.7
C8—C10—H7	109.7	C20—C22—H23	109.4
C8—C10—H8	109.8	C20—C22—H24	109.6
C8—C10—H9	109.4	H22—C22—H23	109.4
H7—C10—H8	109.6	H22—C22—H24	109.4
H7—C10—H9	109.1	H23—C22—H24	109.3
Cu1—O1—C2—C1	−2.3 (6)	N1—Cu1—N2—C18	−116.3 (5)
Cu1—O1—C2—C3	178.8 (3)	N1—Cu1—N2—C19	65.1 (6)
Cu1—O2—C13—C12	−15.6 (7)	N1—C7—C1—C2	2.4 (8)
Cu1—O2—C13—C14	167.7 (3)	N1—C7—C1—C6	−179.9 (5)
Cu1—N1—C7—C1	5.0 (7)	N1—C8—C9—C11	63.0 (9)
Cu1—N1—C8—C9	−126.2 (5)	N2—Cu1—O1—C2	165.7 (4)
Cu1—N1—C8—C10	108.3 (5)	N2—Cu1—O2—C13	20.6 (4)
Cu1—N2—C18—C12	5.2 (7)	N2—Cu1—N1—C7	−107.6 (5)
Cu1—N2—C19—C20	−118.4 (5)	N2—Cu1—N1—C8	75.1 (6)
Cu1—N2—C19—C21	115.6 (5)	N2—C18—C12—C13	6.5 (8)
Cl1—C3—C2—O1	0.0 (6)	N2—C18—C12—C17	−175.9 (5)
Cl1—C3—C2—C1	−179.0 (3)	N2—C19—C20—C22	57.4 (8)
Cl1—C3—C4—C5	−179.4 (4)	C1—C2—C3—C4	1.3 (7)
Cl2—C5—C4—C3	179.7 (4)	C1—C6—C5—C4	−1.3 (7)
Cl2—C5—C6—C1	178.7 (4)	C1—C7—N1—C8	−177.7 (5)
Cl3—C14—C13—O2	−1.2 (6)	C2—C1—C6—C5	3.0 (7)
Cl3—C14—C13—C12	−178.2 (4)	C2—C3—C4—C5	0.3 (7)
Cl3—C14—C15—C16	179.4 (5)	C3—C2—C1—C6	−2.8 (6)
Cl4—C16—C15—C14	−178.3 (5)	C3—C2—C1—C7	174.9 (4)
Cl4—C16—C17—C12	177.5 (5)	C3—C4—C5—C6	−0.3 (7)
O1—Cu1—O2—C13	−77.1 (6)	C5—C6—C1—C7	−174.8 (5)
O1—Cu1—N1—C7	−8.1 (4)	C7—N1—C8—C9	56.4 (7)
O1—Cu1—N1—C8	174.7 (4)	C7—N1—C8—C10	−69.1 (6)
O1—Cu1—N2—C18	143.7 (4)	C10—C8—C9—C11	−173.4 (7)
O1—Cu1—N2—C19	−34.9 (3)	C12—C13—C14—C15	1.5 (8)
O1—C2—C1—C6	178.2 (4)	C12—C17—C16—C15	0 (1)
O1—C2—C1—C7	−4.0 (7)	C12—C18—N2—C19	−176.2 (5)
O1—C2—C3—C4	−179.8 (4)	C13—C12—C17—C16	1.7 (9)
O2—Cu1—O1—C2	−96.4 (5)	C13—C14—C15—C16	−0.4 (9)
O2—Cu1—N1—C7	151.2 (4)	C14—C13—C12—C17	−2.2 (7)
O2—Cu1—N1—C8	−26.1 (4)	C14—C13—C12—C18	175.4 (5)
O2—Cu1—N2—C18	−15.2 (4)	C14—C15—C16—C17	0 (1)
O2—Cu1—N2—C19	166.3 (3)	C16—C17—C12—C18	−175.9 (6)
O2—C13—C12—C17	−179.0 (5)	C18—N2—C19—C20	63.0 (7)
O2—C13—C12—C18	−1.5 (8)	C18—N2—C19—C21	−63.0 (6)
O2—C13—C14—C15	178.6 (5)	C21—C19—C20—C22	−177.9 (6)
N1—Cu1—O1—C2	7.0 (4)	C21—C19—C20—C22	−177.9 (6)
N1—Cu1—O2—C13	179.4 (4)