Carbon dioxide capture from air leading to bis­[N-(5-methyl-1H-pyrazol-3-yl-κN²)carbamato-κO]copper(II) tetra­hydrate

A mononuclear square-planar Cu^II complex was synthesized by reacting 5-methyl-3-pyrazolamine and copper(II) acetate in water under ambient conditions. Di­ethano­lamine was added to facilitate carbon dioxide adsorption, creating an alkaline environment. Structural analysis revealed that the complex crystallizes in the P2₁/c space group of the monoclinic crystal system, with the central copper(II) atom in a square-planar coordination environment N₂O₂. Co-crystallized water mol­ecules are present, forming O—H...O hydrogen bonds with the Cu^II mononuclear complex. Hirshfeld surface analysis highlighted the importance of various inter­actions, including H...O/O...H, H...C/C...H, and H...N/N...H, in providing crystal structure packing.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.041
• wR factor = 0.118
• Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT417_ALERT_2_C Short Inter D-H..H-D       H3A      ..H4D      .       2.11 Ang.
                                            1-x,1/2+y,1/2-z  =      2_655 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          2 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          2 Note
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          6 Report
PLAT173_ALERT_4_G The CIF-Embedded .res File Contains DANG Records          2 Report
PLAT802_ALERT_4_G CIF Input Record(s) with more than 80 Characters          1 Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         83 Note
PLAT941_ALERT_3_G Average HKL Measurement Multiplicity ...........        3.2 Low
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
   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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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Computing details

Data collection: CrysAlis PRO 1.171.42.93a (Rigaku OD, 2023); cell refinement: CrysAlis PRO 1.171.42.93a (Rigaku OD, 2023); data reduction: CrysAlis PRO 1.171.42.93a (Rigaku OD, 2023); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015b); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015a); molecular graphics: Olex2 1.5 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 1.5 (Dolomanov et al., 2009).

Bis[N-(5-methyl-1H-pyrazol-3-yl-κN²)carbamato-κO]copper(II) tetrahydrate

Crystal data

[Cu(C5H6N3O2)2]·4H2O	F(000) = 430
Mr = 415.86	Dx = 1.675 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 8.4623 (2) Å	Cell parameters from 2285 reflections
b = 5.64870 (16) Å	θ = 5.1–72.3°
c = 17.4536 (4) Å	µ = 2.39 mm^−1
β = 98.786 (2)°	T = 200 K
V = 824.51 (4) Å^3	Block, clear light violet
Z = 2	0.15 × 0.15 × 0.15 mm

Data collection

XtaLAB Synergy, Dualflex, HyPix diffractometer	1401 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	Rint = 0.042
ω scans	θmax = 76.8°, θmin = 5.1°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2023)	h = −10→10
Tmin = 0.638, Tmax = 1.000	k = −6→4
5223 measured reflections	l = −16→22
1634 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.118	w = 1/[σ^2(Fo^2) + (0.0636P)^2 + 0.4306P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
1634 reflections	Δρmax = 0.45 e Å^−3
116 parameters	Δρmin = −0.57 e Å^−3
2 restraints

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	0.000000	0.000000	0.000000	0.0327 (2)
O4	0.6601 (3)	0.2829 (4)	0.29517 (11)	0.0518 (6)
H4D	0.663197	0.160498	0.265176	0.078*
H4E	0.733747	0.377068	0.282986	0.078*
N2	−0.2338 (3)	0.3798 (4)	−0.05018 (12)	0.0354 (5)
H2	−0.253149	0.326001	−0.098018	0.042*
N1	−0.1348 (2)	0.2716 (4)	0.00870 (11)	0.0331 (5)
N3	−0.0507 (3)	0.3550 (4)	0.14235 (11)	0.0362 (5)
H3	−0.059104	0.455034	0.180169	0.043*
O3	0.3513 (3)	0.4313 (5)	0.30719 (12)	0.0567 (6)
H3A	0.280457	0.334940	0.282998	0.085*
H3B	0.442727	0.365820	0.303128	0.085*
C1	−0.1376 (3)	0.4090 (5)	0.07052 (14)	0.0327 (5)
C2	−0.2365 (3)	0.6047 (5)	0.05156 (15)	0.0368 (6)
H2A	−0.257394	0.729896	0.084961	0.044*
C4	−0.4112 (3)	0.7265 (6)	−0.07931 (17)	0.0455 (7)
H4A	−0.388986	0.707721	−0.132463	0.068*
H4B	−0.398069	0.893005	−0.063909	0.068*
H4C	−0.521048	0.676241	−0.076675	0.068*
C3	−0.2977 (3)	0.5781 (5)	−0.02590 (15)	0.0360 (6)
C5	0.0462 (3)	0.1642 (5)	0.16088 (13)	0.0339 (6)
O1	0.0677 (2)	0.0130 (3)	0.10968 (10)	0.0391 (5)
O2	0.1152 (2)	0.1456 (4)	0.22973 (9)	0.0400 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0378 (3)	0.0405 (4)	0.0182 (3)	0.0035 (2)	−0.0012 (2)	−0.0008 (2)
O4	0.0577 (12)	0.0586 (14)	0.0355 (10)	−0.0059 (11)	−0.0042 (9)	−0.0031 (9)
N2	0.0403 (11)	0.0409 (13)	0.0228 (10)	0.0015 (10)	−0.0020 (8)	0.0030 (9)
N1	0.0363 (11)	0.0417 (12)	0.0200 (9)	0.0032 (9)	−0.0003 (8)	0.0016 (9)
N3	0.0442 (12)	0.0438 (13)	0.0196 (9)	0.0015 (10)	0.0016 (8)	−0.0031 (9)
O3	0.0618 (14)	0.0628 (14)	0.0418 (12)	−0.0098 (12)	−0.0036 (10)	0.0008 (11)
C1	0.0341 (12)	0.0392 (14)	0.0245 (11)	−0.0040 (11)	0.0036 (9)	−0.0001 (11)
C2	0.0393 (13)	0.0412 (15)	0.0296 (12)	0.0004 (12)	0.0046 (10)	−0.0009 (11)
C4	0.0419 (14)	0.0491 (18)	0.0435 (15)	0.0032 (13)	−0.0004 (12)	0.0085 (13)
C3	0.0352 (12)	0.0391 (14)	0.0336 (13)	−0.0027 (11)	0.0048 (10)	0.0041 (12)
C5	0.0409 (13)	0.0417 (14)	0.0187 (11)	−0.0064 (12)	0.0031 (9)	0.0000 (10)
O1	0.0478 (11)	0.0465 (12)	0.0205 (9)	0.0065 (8)	−0.0028 (8)	−0.0009 (7)
O2	0.0491 (10)	0.0501 (11)	0.0183 (8)	−0.0039 (9)	−0.0026 (7)	0.0022 (8)

Geometric parameters (Å, º)

Cu1—N1	1.931 (2)	N3—C5	1.363 (4)
Cu1—N1^i	1.931 (2)	O3—H3A	0.8697
Cu1—O1	1.9140 (17)	O3—H3B	0.8700
Cu1—O1^i	1.9140 (17)	C1—C2	1.396 (4)
O4—H4D	0.8701	C2—H2A	0.9500
O4—H4E	0.8698	C2—C3	1.380 (4)
N2—H2	0.8800	C4—H4A	0.9800
N2—N1	1.367 (3)	C4—H4B	0.9800
N2—C3	1.341 (4)	C4—H4C	0.9800
N1—C1	1.333 (3)	C4—C3	1.490 (4)
N3—H3	0.8800	C5—O1	1.269 (3)
N3—C1	1.387 (3)	C5—O2	1.258 (3)
N1^i—Cu1—N1	180.0	N1—C1—C2	110.7 (2)
O1^i—Cu1—N1^i	88.92 (8)	N3—C1—C2	127.2 (2)
O1^i—Cu1—N1	91.08 (8)	C1—C2—H2A	127.2
O1—Cu1—N1	88.92 (8)	C3—C2—C1	105.5 (2)
O1—Cu1—N1^i	91.08 (8)	C3—C2—H2A	127.2
O1—Cu1—O1^i	180.0	H4A—C4—H4B	109.5
H4D—O4—H4E	104.5	H4A—C4—H4C	109.5
N1—N2—H2	124.3	H4B—C4—H4C	109.5
C3—N2—H2	124.3	C3—C4—H4A	109.5
C3—N2—N1	111.5 (2)	C3—C4—H4B	109.5
N2—N1—Cu1	126.70 (16)	C3—C4—H4C	109.5
C1—N1—Cu1	127.60 (17)	N2—C3—C2	107.0 (2)
C1—N1—N2	105.3 (2)	N2—C3—C4	121.7 (2)
C1—N3—H3	116.4	C2—C3—C4	131.4 (3)
C5—N3—H3	116.4	O1—C5—N3	120.7 (2)
C5—N3—C1	127.2 (2)	O2—C5—N3	117.9 (2)
H3A—O3—H3B	104.5	O2—C5—O1	121.4 (3)
N1—C1—N3	122.1 (2)	C5—O1—Cu1	132.59 (17)
Cu1—N1—C1—N3	−7.3 (4)	C1—N3—C5—O1	1.3 (4)
Cu1—N1—C1—C2	172.53 (18)	C1—N3—C5—O2	−179.9 (2)
N2—N1—C1—N3	179.7 (2)	C1—C2—C3—N2	−1.3 (3)
N2—N1—C1—C2	−0.4 (3)	C1—C2—C3—C4	179.3 (3)
N1—N2—C3—C2	1.1 (3)	C3—N2—N1—Cu1	−173.46 (18)
N1—N2—C3—C4	−179.4 (2)	C3—N2—N1—C1	−0.5 (3)
N1—C1—C2—C3	1.1 (3)	C5—N3—C1—N1	0.0 (4)
N3—C1—C2—C3	−179.1 (3)	C5—N3—C1—C2	−179.9 (3)
N3—C5—O1—Cu1	5.3 (4)	O2—C5—O1—Cu1	−173.44 (18)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4D···O3^ii	0.87	1.80	2.664 (3)	171
O4—H4E···O1^iii	0.87	2.44	2.930 (3)	116
O4—H4E···O2^iii	0.87	2.02	2.873 (3)	167
N2—H2···O4^iv	0.88	1.99	2.863 (3)	169
N3—H3···O2^v	0.88	2.02	2.889 (3)	169
O3—H3A···O2	0.87	1.89	2.756 (3)	176
O3—H3B···O4	0.87	1.92	2.783 (3)	169
C2—H2A···O3^v	0.95	2.43	3.340 (4)	159

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