A bis-chelate o-vanillin-2-ethano­lamine copper(II) complex bearing both imine and amine forms of the ligand

The copper(II) atom in the mol­ecular title complex has a distorted square-pyramidal coordination environment by three O and two N atoms from a bidentate and a tridentate ligand.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.032
• wR factor = 0.079
• Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Theta(Min).          7 Note
PLAT915_ALERT_3_C No Flack x Check Done: Low Friedel Pair Coverage         51 %

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
PLAT792_ALERT_1_G Model has Chirality at N2          (Polar  SPGR)          R Verify
PLAT794_ALERT_5_G Tentative Bond Valency for Cu1       (II)      .       2.15 Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        312 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          2 Note
PLAT951_ALERT_5_G Calculated (ThMax) and CIF-Reported Kmax Differ           2 Units
PLAT957_ALERT_1_G Calculated (ThMax) and Actual (FCF) Kmax Differ           2 Units
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
   8 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   3 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 OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

(2-{[(2-Hydroxyethyl-κO)amino-κN]methyl}-6-methoxyphenolato-κO)(2-{[(2-hydroxyethyl)imino-κN]methyl}-6-methoxyphenolato-κO)copper(II)

Crystal data

[Cu(C10H14NO3)(C10H12NO3)]	Dx = 1.472 Mg m^−3
Mr = 453.97	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 4616 reflections
a = 8.3068 (9) Å	θ = 4.1–28.6°
b = 24.3280 (19) Å	µ = 1.11 mm^−1
c = 10.1370 (9) Å	T = 150 K
V = 2048.6 (3) Å^3	Plate, green
Z = 4	0.31 × 0.15 × 0.05 mm
F(000) = 948

Data collection

New Gemini, Dual, Cu at zero, Atlas diffractometer	3777 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	3539 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
Detector resolution: 10.6426 pixels mm^-1	θmax = 28.8°, θmin = 3.5°
ω scans	h = −10→9
Absorption correction: analytical (CrysAlisPro; Rigaku OD, 2015)	k = −31→31
Tmin = 0.509, Tmax = 0.855	l = −13→12
10546 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.032	w = 1/[σ^2(Fo^2) + (0.0466P)^2 + 0.2171P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.079	(Δ/σ)max = 0.002
S = 1.06	Δρmax = 0.31 e Å^−3
3777 reflections	Δρmin = −0.38 e Å^−3
268 parameters	Absolute structure: Classical Flack method preferred over Parsons because s.u. lower
1 restraint	Absolute structure parameter: −0.011 (15)

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. 1. Fixed Uiso At 1.2 times of: All C(H) groups, All C(H,H) groups, All N(H) groups At 1.5 times of: All C(H,H,H) groups, All O(H) groups 2.a Ternary CH refined with riding coordinates: N2(H2) 2.b Secondary CH2 refined with riding coordinates: C9(H9A,H9B), C10(H10A,H10B), C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B) 2.c Aromatic/amide H refined with riding coordinates: C3(H3A), C4(H4), C5(H5), C8(H8), C13(H13), C14(H14), C15(H15) 2.d Idealised Me refined as rotating group: C1(H1A,H1B,H1C), C11(H11A,H11B,H11C) 2.e Idealised tetrahedral OH refined as rotating group: O3(H3)

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

	x	y	z	Uiso*/Ueq
Cu1	0.71596 (4)	0.50706 (2)	0.41167 (6)	0.01347 (11)
O1	0.3846 (3)	0.37604 (10)	0.2532 (3)	0.0268 (6)
O2	0.5898 (3)	0.44465 (9)	0.3556 (2)	0.0194 (5)
O3	0.8418 (3)	0.47888 (13)	0.8013 (3)	0.0303 (6)
H3	0.910708	0.461250	0.840828	0.045*
O4	1.0725 (3)	0.63655 (10)	0.5057 (3)	0.0219 (5)
O5	0.8755 (2)	0.56419 (8)	0.4016 (3)	0.0176 (5)
O6	0.5411 (3)	0.52613 (11)	0.5985 (3)	0.0187 (5)
H6	0.567 (5)	0.5466 (18)	0.649 (5)	0.028*
N1	0.8651 (3)	0.46065 (12)	0.5178 (3)	0.0154 (6)
N2	0.5490 (3)	0.55538 (11)	0.3227 (3)	0.0155 (6)
H2	0.475620	0.530360	0.276506	0.019*
C1	0.2700 (6)	0.33956 (19)	0.1958 (5)	0.0428 (12)
H1A	0.200504	0.359757	0.137664	0.064*
H1B	0.206937	0.322833	0.264295	0.064*
H1C	0.325208	0.311543	0.146868	0.064*
C2	0.4986 (4)	0.35356 (15)	0.3365 (3)	0.0196 (7)
C3	0.5087 (5)	0.29840 (15)	0.3675 (3)	0.0245 (8)
H3A	0.434851	0.273654	0.332428	0.029*
C4	0.6303 (5)	0.27994 (15)	0.4515 (4)	0.0303 (9)
H4	0.636593	0.242899	0.473592	0.036*
C5	0.7397 (5)	0.31605 (16)	0.5012 (4)	0.0255 (8)
H5	0.821347	0.303071	0.555711	0.031*
C6	0.7321 (4)	0.37315 (15)	0.4720 (3)	0.0187 (7)
C7	0.6087 (4)	0.39289 (12)	0.3878 (3)	0.0155 (7)
C8	0.8504 (4)	0.40836 (15)	0.5316 (3)	0.0184 (7)
H8	0.924904	0.391349	0.586611	0.022*
C9	0.9906 (5)	0.48739 (15)	0.5970 (4)	0.0208 (8)
H9A	1.048384	0.513686	0.542842	0.025*
H9B	1.066860	0.460018	0.627594	0.025*
C10	0.9173 (5)	0.51648 (16)	0.7138 (4)	0.0246 (8)
H10A	1.000746	0.536379	0.760726	0.029*
H10B	0.838544	0.542958	0.682967	0.029*
C11	1.1634 (5)	0.67643 (17)	0.5768 (4)	0.0309 (9)
H11A	1.234707	0.695184	0.517408	0.046*
H11B	1.225148	0.658469	0.644258	0.046*
H11C	1.091562	0.702508	0.616645	0.046*
C12	0.9635 (3)	0.65617 (12)	0.4146 (4)	0.0180 (6)
C13	0.9540 (4)	0.71095 (14)	0.3758 (4)	0.0247 (8)
H13	1.025083	0.736751	0.410207	0.030*
C14	0.8373 (5)	0.72677 (16)	0.2852 (4)	0.0294 (9)
H14	0.832475	0.763044	0.256536	0.035*
C15	0.7285 (5)	0.68872 (16)	0.2376 (4)	0.0249 (8)
H15	0.648537	0.699987	0.179372	0.030*
C16	0.7364 (4)	0.63357 (14)	0.2756 (3)	0.0172 (7)
C17	0.8560 (4)	0.61619 (13)	0.3639 (3)	0.0156 (7)
C18	0.6167 (4)	0.59254 (15)	0.2197 (3)	0.0191 (7)
H18A	0.529395	0.612378	0.177709	0.023*
H18B	0.669693	0.570550	0.152753	0.023*
C19	0.4499 (4)	0.58501 (13)	0.4204 (4)	0.0201 (7)
H19A	0.354505	0.599835	0.378298	0.024*
H19B	0.510825	0.615315	0.457572	0.024*
C20	0.4019 (4)	0.54520 (15)	0.5289 (4)	0.0220 (8)
H20A	0.329361	0.563357	0.589924	0.026*
H20B	0.345529	0.514124	0.490604	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01244 (19)	0.01677 (18)	0.01119 (17)	0.00087 (13)	−0.0031 (2)	0.0002 (3)
O1	0.0330 (15)	0.0203 (12)	0.0270 (14)	−0.0059 (11)	−0.0155 (11)	0.0038 (11)
O2	0.0223 (13)	0.0170 (11)	0.0191 (11)	0.0016 (10)	−0.0084 (10)	0.0035 (10)
O3	0.0191 (13)	0.0563 (18)	0.0155 (12)	0.0059 (14)	−0.0001 (11)	0.0035 (13)
O4	0.0167 (12)	0.0237 (12)	0.0254 (12)	−0.0012 (10)	−0.0079 (11)	−0.0016 (11)
O5	0.0133 (10)	0.0172 (9)	0.0224 (11)	0.0013 (8)	−0.0023 (12)	0.0018 (13)
O6	0.0148 (13)	0.0261 (13)	0.0152 (11)	0.0016 (10)	−0.0013 (10)	−0.0025 (11)
N1	0.0091 (13)	0.0265 (15)	0.0107 (12)	0.0014 (11)	−0.0009 (10)	0.0005 (12)
N2	0.0123 (13)	0.0199 (14)	0.0143 (12)	−0.0019 (11)	−0.0028 (11)	−0.0014 (12)
C1	0.047 (3)	0.032 (2)	0.049 (3)	−0.017 (2)	−0.029 (2)	0.006 (2)
C2	0.0239 (19)	0.0221 (17)	0.0126 (15)	0.0020 (14)	−0.0013 (14)	0.0024 (14)
C3	0.030 (2)	0.0193 (16)	0.0239 (17)	−0.0026 (15)	−0.0004 (15)	−0.0018 (15)
C4	0.037 (2)	0.0180 (17)	0.036 (2)	0.0062 (16)	−0.0021 (17)	0.0066 (16)
C5	0.028 (2)	0.0234 (19)	0.0253 (18)	0.0093 (15)	−0.0033 (16)	0.0062 (17)
C6	0.0193 (18)	0.0226 (18)	0.0143 (17)	0.0049 (14)	0.0016 (13)	0.0019 (15)
C7	0.0187 (16)	0.0168 (13)	0.0109 (17)	0.0015 (12)	0.0027 (12)	0.0024 (13)
C8	0.0133 (17)	0.0290 (19)	0.0131 (15)	0.0095 (14)	0.0000 (13)	0.0046 (15)
C9	0.0138 (18)	0.033 (2)	0.0157 (16)	−0.0009 (15)	−0.0048 (15)	0.0074 (16)
C10	0.024 (2)	0.0272 (19)	0.0228 (18)	0.0012 (17)	−0.0099 (17)	−0.0019 (16)
C11	0.029 (2)	0.029 (2)	0.035 (2)	−0.0051 (17)	−0.0109 (18)	−0.0042 (18)
C12	0.0134 (14)	0.0215 (14)	0.0191 (14)	0.0022 (11)	0.0007 (17)	0.000 (2)
C13	0.0205 (18)	0.0205 (15)	0.033 (2)	−0.0040 (13)	0.0023 (15)	0.0013 (15)
C14	0.027 (2)	0.0220 (18)	0.039 (2)	0.0011 (16)	0.0012 (18)	0.0126 (17)
C15	0.0217 (19)	0.027 (2)	0.025 (2)	0.0035 (15)	−0.0027 (15)	0.0091 (17)
C16	0.0152 (17)	0.0231 (17)	0.0132 (16)	0.0018 (13)	0.0022 (13)	0.0021 (15)
C17	0.0144 (16)	0.0184 (15)	0.0139 (14)	0.0030 (13)	0.0054 (12)	0.0038 (13)
C18	0.0179 (18)	0.0265 (18)	0.0129 (15)	0.0031 (14)	−0.0018 (13)	0.0026 (15)
C19	0.0137 (15)	0.0221 (14)	0.0245 (17)	0.0014 (11)	0.0019 (16)	−0.0019 (19)
C20	0.0126 (18)	0.0302 (19)	0.0232 (18)	0.0016 (14)	0.0009 (14)	0.0037 (16)

Geometric parameters (Å, º)

Cu1—O2	1.930 (2)	C5—C6	1.422 (5)
Cu1—O5	1.923 (2)	C6—C7	1.417 (5)
Cu1—O6	2.432 (3)	C6—C8	1.437 (5)
Cu1—N1	1.992 (3)	C8—H8	0.9300
Cu1—N2	2.030 (3)	C9—H9A	0.9700
O1—C1	1.426 (5)	C9—H9B	0.9700
O1—C2	1.382 (4)	C9—C10	1.508 (5)
O2—C7	1.310 (4)	C10—H10A	0.9700
O3—H3	0.8200	C10—H10B	0.9700
O3—C10	1.420 (5)	C11—H11A	0.9600
O4—C11	1.425 (4)	C11—H11B	0.9600
O4—C12	1.379 (4)	C11—H11C	0.9600
O5—C17	1.332 (4)	C12—C13	1.392 (5)
O6—H6	0.75 (5)	C12—C17	1.417 (5)
O6—C20	1.432 (4)	C13—H13	0.9300
N1—C8	1.286 (5)	C13—C14	1.390 (5)
N1—C9	1.467 (5)	C14—H14	0.9300
N2—H2	0.9800	C14—C15	1.381 (6)
N2—C18	1.491 (4)	C15—H15	0.9300
N2—C19	1.476 (4)	C15—C16	1.397 (5)
C1—H1A	0.9600	C16—C17	1.402 (5)
C1—H1B	0.9600	C16—C18	1.518 (5)
C1—H1C	0.9600	C18—H18A	0.9700
C2—C3	1.381 (5)	C18—H18B	0.9700
C2—C7	1.422 (5)	C19—H19A	0.9700
C3—H3A	0.9300	C19—H19B	0.9700
C3—C4	1.396 (5)	C19—C20	1.519 (5)
C4—H4	0.9300	C20—H20A	0.9700
C4—C5	1.360 (6)	C20—H20B	0.9700
C5—H5	0.9300
O2—Cu1—O6	93.16 (10)	N1—C9—H9A	109.5
O2—Cu1—N1	92.92 (11)	N1—C9—H9B	109.5
O2—Cu1—N2	87.35 (11)	N1—C9—C10	110.5 (3)
O5—Cu1—O2	157.96 (12)	H9A—C9—H9B	108.1
O5—Cu1—O6	108.36 (10)	C10—C9—H9A	109.5
O5—Cu1—N1	90.55 (10)	C10—C9—H9B	109.5
O5—Cu1—N2	91.65 (10)	O3—C10—C9	111.5 (3)
N1—Cu1—O6	93.37 (10)	O3—C10—H10A	109.3
N1—Cu1—N2	173.44 (11)	O3—C10—H10B	109.3
N2—Cu1—O6	80.08 (10)	C9—C10—H10A	109.3
C2—O1—C1	117.4 (3)	C9—C10—H10B	109.3
C7—O2—Cu1	128.1 (2)	H10A—C10—H10B	108.0
C10—O3—H3	109.5	O4—C11—H11A	109.5
C12—O4—C11	116.8 (3)	O4—C11—H11B	109.5
C17—O5—Cu1	128.2 (2)	O4—C11—H11C	109.5
Cu1—O6—H6	119 (3)	H11A—C11—H11B	109.5
C20—O6—Cu1	99.2 (2)	H11A—C11—H11C	109.5
C20—O6—H6	111 (3)	H11B—C11—H11C	109.5
C8—N1—Cu1	124.1 (2)	O4—C12—C13	123.9 (3)
C8—N1—C9	116.5 (3)	O4—C12—C17	114.8 (3)
C9—N1—Cu1	119.1 (2)	C13—C12—C17	121.2 (3)
Cu1—N2—H2	106.1	C12—C13—H13	120.3
C18—N2—Cu1	113.8 (2)	C14—C13—C12	119.5 (3)
C18—N2—H2	106.1	C14—C13—H13	120.3
C19—N2—Cu1	111.4 (2)	C13—C14—H14	119.9
C19—N2—H2	106.1	C15—C14—C13	120.1 (3)
C19—N2—C18	112.6 (3)	C15—C14—H14	119.9
O1—C1—H1A	109.5	C14—C15—H15	119.4
O1—C1—H1B	109.5	C14—C15—C16	121.1 (3)
O1—C1—H1C	109.5	C16—C15—H15	119.4
H1A—C1—H1B	109.5	C15—C16—C17	119.9 (3)
H1A—C1—H1C	109.5	C15—C16—C18	119.8 (3)
H1B—C1—H1C	109.5	C17—C16—C18	120.2 (3)
O1—C2—C7	113.5 (3)	O5—C17—C12	118.1 (3)
C3—C2—O1	124.4 (3)	O5—C17—C16	123.8 (3)
C3—C2—C7	122.1 (3)	C16—C17—C12	118.1 (3)
C2—C3—H3A	120.2	N2—C18—C16	112.7 (3)
C2—C3—C4	119.7 (3)	N2—C18—H18A	109.1
C4—C3—H3A	120.2	N2—C18—H18B	109.1
C3—C4—H4	119.9	C16—C18—H18A	109.1
C5—C4—C3	120.1 (3)	C16—C18—H18B	109.1
C5—C4—H4	119.9	H18A—C18—H18B	107.8
C4—C5—H5	119.2	N2—C19—H19A	109.9
C4—C5—C6	121.6 (4)	N2—C19—H19B	109.9
C6—C5—H5	119.2	N2—C19—C20	108.7 (3)
C5—C6—C8	117.7 (3)	H19A—C19—H19B	108.3
C7—C6—C5	119.2 (3)	C20—C19—H19A	109.9
C7—C6—C8	123.1 (3)	C20—C19—H19B	109.9
O2—C7—C2	118.6 (3)	O6—C20—C19	110.6 (3)
O2—C7—C6	124.2 (3)	O6—C20—H20A	109.5
C6—C7—C2	117.2 (3)	O6—C20—H20B	109.5
N1—C8—C6	127.5 (3)	C19—C20—H20A	109.5
N1—C8—H8	116.2	C19—C20—H20B	109.5
C6—C8—H8	116.2	H20A—C20—H20B	108.1
Cu1—O2—C7—C2	178.7 (2)	C5—C6—C7—C2	−0.3 (5)
Cu1—O2—C7—C6	−0.9 (5)	C5—C6—C8—N1	179.7 (3)
Cu1—O5—C17—C12	153.4 (3)	C7—C2—C3—C4	−0.1 (5)
Cu1—O5—C17—C16	−27.4 (5)	C7—C6—C8—N1	−1.2 (6)
Cu1—O6—C20—C19	−44.8 (3)	C8—N1—C9—C10	−102.7 (3)
Cu1—N1—C8—C6	2.6 (5)	C8—C6—C7—O2	0.2 (5)
Cu1—N1—C9—C10	71.2 (3)	C8—C6—C7—C2	−179.4 (3)
Cu1—N2—C18—C16	−62.6 (3)	C9—N1—C8—C6	176.1 (3)
Cu1—N2—C19—C20	−44.5 (3)	C11—O4—C12—C13	9.3 (5)
O1—C2—C3—C4	179.1 (3)	C11—O4—C12—C17	−169.1 (3)
O1—C2—C7—O2	1.8 (4)	C12—C13—C14—C15	2.2 (6)
O1—C2—C7—C6	−178.6 (3)	C13—C12—C17—O5	177.7 (3)
O4—C12—C13—C14	−178.6 (3)	C13—C12—C17—C16	−1.6 (5)
O4—C12—C17—O5	−3.9 (5)	C13—C14—C15—C16	−2.2 (6)
O4—C12—C17—C16	176.9 (3)	C14—C15—C16—C17	0.3 (6)
N1—C9—C10—O3	63.7 (4)	C14—C15—C16—C18	−179.0 (3)
N2—C19—C20—O6	63.9 (4)	C15—C16—C17—O5	−177.6 (3)
C1—O1—C2—C3	0.1 (5)	C15—C16—C17—C12	1.5 (5)
C1—O1—C2—C7	179.4 (4)	C15—C16—C18—N2	−134.9 (3)
C2—C3—C4—C5	−0.9 (6)	C17—C12—C13—C14	−0.3 (6)
C3—C2—C7—O2	−178.9 (3)	C17—C16—C18—N2	45.8 (4)
C3—C2—C7—C6	0.7 (5)	C18—N2—C19—C20	−173.8 (3)
C3—C4—C5—C6	1.3 (6)	C18—C16—C17—O5	1.6 (5)
C4—C5—C6—C7	−0.7 (6)	C18—C16—C17—C12	−179.2 (3)
C4—C5—C6—C8	178.5 (4)	C19—N2—C18—C16	65.4 (3)
C5—C6—C7—O2	179.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O5^i	0.82	1.98	2.766 (3)	161
O6—H6···O1^ii	0.75 (5)	2.19 (5)	2.916 (4)	163 (5)
N2—H2···O6^iii	0.98	2.27	3.107 (4)	142

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